Benzaldehyde oxime derivatives, production and use thereof

ABSTRACT

The present invention relates to novel benzaldehyde derivatives, specifically α-azolyl-2-substituted benzaldehyde oxime derivatives, their production, and fungicidal, herbicidal and growth regulating compositions containing them.

FIELD OF THE INVENTION

The present invention relates to novel benzaldehyde oxime derivatives, specifically α-azolyl-2-substituted benzaldehyde oxime derivatives, their production, and fungicidal, herbicidal and growth regulating compositions containing them.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 4,599,348 (JP-A 60-87269), JP-A 1-308260, JP-A 3-68559, JP-A 5-1046 and W092/09581 disclose α-azolylbenzaldehyde oxime derivatives and their insecticidal and fungicidal activities. There is still a need for compounds having superior activity, utility, etc., as well as low toxicity.

OBJECTS OF THE INVENTION

The main object of the present invention is to provide novel compounds having excellent fungicidal, herbicidal and growth regulating activities.

Another object of the present invention is to provide processes for producing the above novel compounds.

Another object of the present invention is to provide novel fungicidal, herbicidal and growth regulating compositions.

These objects as well as other objects and advantages of the present invention will become apparent to those skilled in the art from the following description.

SUMMARY OF THE INVENTION

The present inventors have intensively studied to achieve the above objects. As a result, it has been found that novel benzaldehyde oxime derivatives having various groups attached to their 2-position via an oxygen atom or sulfur atom, specifically α-azolyl-2-substituted benzaldehyde oxime derivatives, have excellent herbicidal activity, growth regulating activity, particularly growth inhibiting activity, as well as excellent fungicidal activity.

That is, the present invention provides a compound of the formula (I): ##STR1## wherein R¹ is alkoxycarbonylalkyl, optionally substituted acylalkyl, optionally substituted phenyl, optionally substituted phenylalkyl, optionally substituted phenoxyalkyl, an optionally substituted heterocyclic group or optionally substituted heterocyclic alkyl; R² is hydrogen, alkyl, alkenyl, alkynyl, halogenated alkyl, halogenated alkenyl, halogenated alkynyl, cycloalkyl, optionally substituted phenyl, optionally substituted benzyl, an optionally substituted heterocyclic group or optionally substituted heterocyclic alkyl; R³ is hydrogen, alkyl, alkoxy or halogen; X is 0 or S; Y is CH or N; and ˜ represents any configuration of the E-isomer, Z-isomer or a mixture of E- and Z-isomers; provided that, when X is 0, R¹ is not optionally substituted phenyl, and that when X is 0, R¹ is not unsubstituted benzyl; or a salt thereof.

The present invention also provides a fungicidal composition comprising as an active ingredient a compound of the formula (I) and an inert carrier or diluent.

The present invention also provides a herbicidal composition comprising as an active ingredient a compound of the formula (I) and an inert carrier or diluent.

The present invention also provides a growth regulating composition comprising as an active ingredient a compound of the formula (I) and an inert carrier or diluent.

The present invention also provides a process for producing a compound of the formula (I): ##STR2## wherein each symbol is as defined above, which comprises reacting a compound of the formula (XIII): ##STR3## wherein each symbol is as defined for the formula (I), with a compound of the formula (III):

    R.sup.1 --L                                                (III)

wherein L is halogen, alkylsulfonyl, alkylsulfonyloxy or arylsulfonyloxy and R^(l) is as defined for the formula (I), in the presence of a base.

The present invention also provides a process for producing a compound of the formula (I): ##STR4## wherein each symbol is as defined above, which comprises reacting a compound of the formula (XI): ##STR5## wherein A is halogen and the other symbol is as defined for the formula (I), with a compound of the formula (XII): ##STR6## wherein Y is as defined for the formula (I), and then, if necessary, reacting the resulting compound with a compound of the formula (XXII):

    R.sup.2 --L                                                (XXII)

wherein L is halogen, alkylsulfonyl, alkylsulfonyloxy or arylsulfonyloxy and R² is as defined for the formula (I) except that R² is not hydrogen, in the presence of a base.

The present invention also provides a process for producing a compound of the formula (I): ##STR7## wherein each symbol is as defined above, which comprises reacting a compound of the formula (X): ##STR8## wherein each symbol is as defined for the formula (I), with a compound of the formula (XIV): ##STR9## wherein W is carbonyl or sulfinyl, Z is chlorine bromine or ##STR10## and Y is as defined for the formula (I).

The present invention also provides a process for producing a compound of the formula (I): ##STR11## wherein each symbol is as defined above, which comprises reacting a compound of the formula (XIII): ##STR12## wherein each symbol is as defined for the formula (I), with a compound of the formula (XXIII):

    R.sup.1 --OH                                               (XXIII)

wherein R¹ is as defined for the formula (I).

DETAILED DESCRIPTION OF THE INVENTION

Examples of the alkoxycarbonylalkyl represented by R¹ include alkoxycarbonylalkyl composed of alkoxycarbonyl having 2 to 6 carbon atoms and alkyl having 1 to 3 carbon atoms, such as methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, etc. In particular, methoxycarbonylmethyl is preferred.

Examples of the optionally substituted acylalkyl represented by R¹ include acylalkyl composed of acyl having 1 to 8 carbon atoms (e.g., formyl, acetyl, propionyl, benzoyl, nicotinoyl, etc.) and alkyl having 1 to 3 carbon atoms, such as acetylmethyl, acetylethyl, benzoylmethyl, benzoylethyl, etc. When the acylalkyl is substituted, the substituent is selected from the same substituents as those of the optionally substituted phenyl represented by R¹ described below. The optionally substituted acylalkyl is preferably benzoylmethyl.

The optionally substituted phenyl represented by R¹ includes unsubstituted phenyl and substituted phenyl. The substituted phenyl has 1 to 5 substituents selected from C₁₋₅ alkyl (e.g., methyl, ethyl, isopropyl, tert-butyl, etc.), C₁₋₄ alkoxy (e.g., methoxy, ethoxy, propoxy, etc.), phenyl, phenoxy, benzyloxy, C₁₋₄ alkylthio (e.g., methylthio, ethylthio, propylthio, etc.), C₁₋₃ alkylsulfonyl (e.g., methylsulfonyl, ethylsulfonyl, propylsulfonyl, etc.), cyano, nitro, halogen (e.g., fluorine, chlorine, bromine, iodine), halogenated C₁₋₃ alkyl (e.g., trifluoromethyl, trichloromethyl, etc.) and halogenated C₁₋₃ alkoxy (e.g., trifluoromethyloxy, trichloromethyloxy, etc.). These substituents may be at any possible position in the phenyl. When X is 0, R¹ is not optionally substituted phenyl.

Examples of the optionally substituted phenylalkyl represented by R¹ include that composed of the above optionally substituted phenyl and alkyl having 1 to 6 carbon atoms, such as phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, etc., each of which may optionally be substituted. Preferred examples of the optionally substituted phenylalkyl include optionally substituted 1-phenylalkyl (e.g., benzyl, 1-phenylethyl, 1-phenylpropyl, etc.), optionally substituted phenethyl, optionally substituted 3-phenylpropyl, etc. When X is 0, the optionally substituted phenylaklyl is not unsubstituted benzyl.

Examples of the optionally substituted phenoxyalkyl represented by R¹ include that composed of optionally substituted phenoxy and alkyl having 1 to 6 carbon atoms, such as phenoxymethyl, phenoxyethyl, phenoxypropyl, phenoxybutyl, etc., each of which may optionally be substituted. Preferred examples of the optionally substituted phenoxyalkyl include 2-phenoxyethyl, 3-phenoxypropyl and 4-phenoxybutyl each of which may optionally be substituted.

The above optionally substituted phenyl or optionally substituted phenoxy may be attached to any possible position of the alkyl. When the phenylalkyl or phenoxyalkyl is substituted, the substituent is selected from the same substituents as those of the optionally substituted phenyl represented by R¹, and the substituent may be at any possible position in the phenyl ring. Preferably, the substituent is selected from C₁₋₅ alkyl (e.g., methyl, ethyl, isopropyl, tert-butyl, etc.), C₁₋₄ alkoxy (e.g., methoxy, ethoxy, propoxy, etc.), halogen (e.g., fluorine, chlorine, bromine, iodine), halogenated C₁₋₃ alkyl (e.g., trifluoromethyl, trichloromethyl, etc.) and halogenated C₁₋₃ alkoxy (e.g., trifluoromethyloxy, trichloromethyloxy, etc.).

Examples of the heterocyclic group of the optionally substituted heterocyclic group represented by R¹ include thienyl (e.g., 2-thienyl, etc.), pyridyl (e.g., 2-pyridyl, etc.), isoxazolyl (e.g., isoxazol-3-yl, isoxazol-5-yl, etc.), benzoxazolyl (e.g., benzoxazol-2-yl, etc.), thiazolyl (e.g., thiazol-2-yl, etc.), benzothiazolyl (e.g., benzothiazol-2-yl, etc.), pyrimidinyl (e.g., pyrimidin-2-yl, pyrimidin-4-yl, etc.), thiadiazolyl (e.g., 1,3,4-thiadiazol-2-yl, etc.), 1,3-dioxolanyl (e.g., 1,3-dioxolan-2-yl, etc.), quinolyl (e.g., 2-quinolyl, etc.), quinoxalinyl (e.g., quinoxalin-2-yl, etc.), etc. In particular, 2-pyridyl is preferred. When the heterocyclic group is substituted, the substituent is selected from the same substituents as those of the optionally substituted phenyl represented by R¹ described above. These substituents may be at any possible position in the heterocyclic group.

Examples of the optionally substituted heterocyclic alkyl represented by R¹ include that composed of the above optionally substituted heterocyclic group represented by R¹ and alkyl having 1 to 4 carbon atoms, such as heterocyclic methyl, heterocyclic ethyl, heterocyclic propyl, etc., each of which may optionally be substituted. In particular, optionally substituted heterocyclic methyl is preferred. The optionally substituted heterocyclic group may be at any possible position in the alkyl. When the heterocyclic group is substituted, the substituent is selected from the same substituents as those of the above optionally substituted phenyl represented by R¹. These substituents may be at any possible position in the heterocyclic group.

R¹ is preferably optionally substituted phenylalkyl, optionally substituted phenoxyalkyl, optionally substituted heterocyclic group or optionally substituted heterocyclic alkyl.

Examples of the alkyl represented by R² include alkyl having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, isobutyl, etc.

Examples of the alkenyl represented by R² include alkenyl having 2 to 6 carbon atoms such as vinyl, allyl, crotyl, etc. In particular, allyl is preferred.

Examples of the alkynyl represented by R² include alkynyl having 2 to 6 carbon atoms such as ethynyl, propynyl, butynyl, etc.

Examples of the halogenated alkyl, halogenated alkenyl and halogenated alkynyl represented by R² include alkyl, alkenyl and alkynyl represented by R² each of which is substituted with at least one halogen (e.g., fluorine, chlorine, bromine, iodine).

Examples of the cycloalkyl represented by R² include cycloalkyl having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

Examples of the optionally substituted phenyl, optionally substituted benzyl, optionally substituted heterocyclic group and optionally substituted heterocyclic alkyl represented by R² include the same groups as those represented by R¹.

R² is preferably alkyl or alkenyl, more preferably methyl, ethyl or allyl.

Examples of the alkyl represented by R³ include alkyl having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc.

Examples of the alkoxy represented by R³ include alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc.

Examples of the halogen represented by R³ include fluorine, chlorine, bromine and iodine.

R³ is preferably hydrogen, alkyl, alkoxy or halogen, more preferably hydrogen, methyl, methoxy, fluorine or chlorine. R³ may be at any possible position in the phenyl, preferably at 5-position in the phenyl.

X is preferably 0.

Y is preferably CH.

Preferred examples of the compounds of the formula (I) include those wherein R¹ is optionally substituted phenylalkyl, optionally substituted phenoxyalkyl or optionally substituted pyridyl; R² is alkyl; R³ is hydrogen, alkyl, alkoxy or halogen; X is 0; and Y is CH.

More preferred examples of the compounds of the formula (I) include:

a compound of the formula (I) wherein R¹ is 4-methylphenylmethyl, R² is methyl, R³ is hydrogen, X is 0, and Y is CH (Compound No. 3);

a compound of the formula (I) wherein R¹ is 2-chlorophenylmethyl, R² is methyl, R³ is hydrogen, X is 0, and Y is CH (Compound No. 7);

a compound of the formula (I) wherein R¹ is 4-methylphenylmethyl, R² is ethyl, R³ is 5-methyl, X is 0, and Y is CH (Compound No. 995);

a compound of the formula (I) wherein R¹ is 1-phenylethyl, R² is methyl, R³ is hydrogen, X is 0, and Y is CH (Compound No. 491);

a compound of the formula (I) wherein R is 1-phenylethyl, R² is methyl, R³ is 5-fluoro, X is 0, and Y is CH (Compound No. 1101);

a compound of the formula (I) wherein R¹ is 5-trifluoromethyl -2-pyridyl, R² is ethyl, R³ is hydrogen, X is 0, and Y is CH (Compound No. 183);

a compound of the formula (I) wherein R¹ is 5-trifluoromethyl -2-pyridyl, R² is methyl, R³ is hydrogen, X is 0, and Y is CH (Compound No. 83);

a compound of the formula (I) wherein R¹ is 5-trifluoromethyl -2-pyridyl, R² is methyl, R³ is 5-chloro, X is 0, and Y is CH (Compound No. 583);

a compound of the formula (I) wherein R¹ is 5-trifluoromethyl -2-pyridyl, R² is methyl, R³ is 5-fluoro, X is 0, and Y is CH (Compound No. 783);

a compound of the formula (I) wherein R¹ is 3,5-dichloro -2-pyridyl, R² is methyl, R³ is 5-chloro, X is 0, and Y is CH (Compound No. 581);

a compound of the formula (I) wherein R¹ is 3-phenylpropyl, R² is methyl, R³ is hydrogen, X is 0, and Y is CH (Compound No. 497);

a compound of the formula (I) wherein R¹ is 2-phenoxylethyl, R² is methyl, R³ is 5-chloro, X is 0, and Y is CH (Compound No. 552);

a compound of the formula (I) wherein R¹ is 2-(4-chlorophenoxy)ethyl, R² is methyl, R³ is hydrogen, X is 0, and Y is CH (Compound No. 863);

a compound of the formula (I) wherein R¹ is 4-phenoxybutyl, R² is methyl, R³ is hydrogen, X is 0, and Y is CH (Compound No. 495); and

a compound of the formula (I) wherein R¹ is 4-phenoxybutyl, R² is ethyl, R³ is hydrogen, X is 0, and Y is CH (Compound No. 876). These compound Nos. are those described in Examples hereinafter.

Each compound of the present invention exists as E-or Z-isomer and includes both of the isomers and mixtures thereof in any mixing ratios. This is indicated by the wave line ˜ in this specification.

The compound of the present invention also includes its hydrochloric acid salt, sulfuric acid salt, nitric acid salt, oxalic acid salt and p-toluenesulfonic acid salt.

The compound of the formula (I) of the present invention can be prepared, for example, according to the following synthetic routes.

Route 1 ##STR13## wherein L is halogen, alkylsulfonyl, alkylsulfonyloxy or arylsulfonyloxy; R⁴ is hydrogen, alkyl or optionally substituted benzyl; and R¹, R³ and X are as defined above.

Examples of the halogen represented by L include chlorine, bromine, iodine, etc. Examples of the alkylsulfonyl represented by L include C₁₋₅ alkylsulfonyl such as methanesulfonyl, ethanesulfonyl, etc. Examples of the alkylsulfonyloxy represented by L include alkylsulfonyloxy having optionally halogenated C₁₋₅ alkyl, such as methanesulfonyloxy, ethanesulfonyloxy, trichloromethanesulfonyloxy, etc. Examples of the arylsulfonyloxy represented by L include optionally substituted benzenesulfonyloxy such as p-toluenesulfonyloxy, benzenesulfonyloxy, etc. Examples of the alkyl represented by R⁴ include alkyl having 1 to 5 carbon atoms such as methyl, ethyl, isopropyl, etc. Examples of the optionally substituted benzyl represented by R⁴ include benzyl optionally substituted with the same substituent(s) as those of the above optionally substituted phenyl represented by R¹, such as benzyl, 4-chlorobenzyl, 4-methylbenzyl, etc.

The compound (IV) can be prepared by reacting the compound (II) with the compound (III) in the presence of a base in the absence of a solvent or in an appropriate solvent.

The amount of the compound (III) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (II).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydride, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (II).

Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g, acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 200° C., preferably 0° C. to 180° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The compound (IV) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Alternatively, the compound (IV) can also be prepared by the following reaction.

Route 1 (continued) ##STR14## wherein each symbol is as defined above.

That is, the compound (IV) can be prepared by reacting the compound (V) with the compound (VI) in the presence of a base in the absence of a solvent or in an appropriate solvent.

The amount of the compound (VI) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (V).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydride, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (II).

Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 200° C., preferably 0° C. to 180° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The compound (IV) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 1 (continued) ##STR15## wherein each symbol is as defined above.

The compound (VII) can be prepared by reacting the compound (IV) with a base or acid in an appropriate solvent to hydrolyze the compound (IV).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), etc. Examples of the acid include hydrochloric acid, sulfuric acid, hydrobromic acid, p-toluenesulfonic acid, etc. The amount of the base or acid to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (IV).

Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 150° C., preferably 0° C. to 120° C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.

The compound (VII) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 1 (continued) ##STR16## wherein A is halogen, and the other symbols are as defined above.

Examples of the halogen represented by A include fluorine, chlorine, bromine and iodine. It is preferably chlorine or bromine.

The compound (VIII) can be prepared by reacting the compound (VII) with a halogenating agent in the absence of a solvent or in an appropriate solvent in the presence or absence of a catalyst.

Examples of the halogenating agent include thionyl halides (e.g., thionyl chloride, thionyl bromide, etc.), phosphoryl halides (e.g., phosphoryl chloride, phosphoryl bromide, etc.), phosphorus halides (e.g., phosphorus pentachloride, phosphorus trichloride, phosphorus pentabromide, phosphorus tribromide, etc.), phosgene, oxalyl halides (e.g., oxalyl chloride, etc.), etc. The amount of the halogenating agent to be used is 1 mol or more, preferably 1 to 10 mol per mol of the compound (VII).

Examples of the catalyst include DMF, DMSO, HMPA, pyridine, triethylamine, iodine, zinc chloride, Viismeier reagent, etc. The amount of the catalyst to be used is 0.005 to 3 mol, preferably 0.01 to 1 mol per mol of the compound

Examples of the reaction solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 150° C., preferably 0° C. to 120° C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.

The compound (VIII) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 1 (continued) ##STR17## wherein each symbol is as defined above.

The compound (X) can be prepared by reacting the compound (VIII) with the compound (IX) or a salt thereof (e.g., hydrochloric acid salt, sulfuric acid salt, etc.) in the presence of a base in the absence of a solvent or in an appropriate solvent.

The amount of the compound (IX) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (VIII).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (VIII).

Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ethers (e.g., THF, dioxane, etc.), water, etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -30° C. to 150° C., preferably -10° C. to 100° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The compound (X) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 1 (continued) ##STR18## wherein each symbol is as defined above.

The compound (XI) can be prepared by reacting the compound (X) with a halogenating agent in the absence of a solvent or in an appropriate solvent.

Examples of the halogenating agent include thionyl halides (e.g., thionyl chloride, thionyl bromide, etc.), phosphoryl halides (e.g., phosphoryl chloride, phosphoryl bromide, etc.), phosphorus halides (e.g., phosphorus pentachloride, phosphorus trichloride, phosphorus pentabromide, phosphorus tribromide, etc.), phosgene, oxalyl halides (e.g., oxalyl chloride, etc.), triphenylphosphine/carbon tetrachloride, triphenylphosphine/carbon tetrabromide, etc. The amount of the halogenating agent to be used is 1 mol or more, preferably 1 to 10 mol per mol of the compound (X).

Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), nitriles (e.g., acetonitrile, propionitrile, etc.), etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -30° C. to 150° C., preferably -10° C. to 120° C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.

The compound (XI) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 1 (continued) ##STR19## wherein each symbol is as defined above.

The compound of the formula (I) of the present invention can be prepared by reacting the compound (XI) with the compound (XII) in the presence or absence of a base in the absence of a solvent or in an appropriate solvent.

The amount of the compound (XII) to be used is 1 mol or more, preferably 1 to 6 mol per mol of the compound (XI).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XI).

Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 200° C., preferably 0° C. to 180° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The desired compound (I) thus obtained can be purified by conventional methods (e.g., chromatography, recrystallization, etc.).

Alternatively, the compound (I) of the present invention can be prepared by the following route.

Route 2 ##STR20## wherein R⁵ is hydrogen, C₁₋₅ alkyl (e.g., methyl, ethyl, isopropyl, etc.) or halogen (e.g., fluorine, chlorine, bromine, iodine), and the other symbols are as defined above.

The compound (XIII) can be prepared by treating the compound (Ia) with a Lewis acid in an appropriate solvent.

Examples of the Lewis acid include aluminium chloride, aluminium bromide, boron trifluoride, boron tribromide, boron trichloride, ferric chloride, etc. In particular, aluminium chloride is preferred. The amount of the Lewis acid to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (Ia).

Examples of the solvent include anisole, nitromethane, nitroethene, etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -50° C. to 150° C., preferably, -20° C. to 100° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The compound (XIII) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 2 (continued) ##STR21## wherein each symbol is as defined above.

The compound of the formula (I) of the present invention can be prepared by reacting the compound (XIII) with the compound (III) in the presence of a base in the absence of a solvent or in an appropriate solvent.

The amount of the compound (III) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XIII).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XIII).

Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 200° C., preferably 0° C. to 180° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The desired compound (I) thus obtained can be purified by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 2 (continued) ##STR22## wherein each symbol is as defined above.

The compound of the formula (I) of the present invention can be prepared by reacting the compound (XIII) with the compound (XXIII) in the presence of triphenylphosphine and diethyl azodicarboxylate or dimethyl azodicarboxylate in the absence of a solvent or in an appropriate solvent.

The amount of the compound (XXIII) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XIII). The amount of the triphenylphosphine to be used is 1 to 5 mol, preferably 1 to 3 mol per mol of the compound (XIII). The amount of the diethyl azodicarboxylate or dimethyl azodicarboxylate to be used is 1 to 5 mol, preferably 1 to 3 mol per mol of the compound (XIII).

Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), nitriles (e.g., acetonitrile, etc.), etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 200° C., preferably 0° C. to 120° C. The reaction time varies with the compounds but is generally 0.5 to 72 hours.

The desired compound (I) thus obtained can be purified by conventional methods (e.g., chromatography, recrystallization, etc.).

Alternatively, the compound (I) of the present invention can be prepared in one step from the intermediate (X) in the above Route 1 (Scheme 6) by the following reaction.

Route 3 ##STR23## wherein W is carbonyl or sulfinyl, Z is chlorine, bromine or ##STR24## and the other symbols are as defined above.

The compound of the formula (I) of the present invention can be prepared by reacting the compound (X) with the compound (XIV) in the absence of a solvent or in an appropriate solvent.

The amount of the compound (XIV) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (X).

Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -30° C. to 150° C., preferably -10° C. to 120° C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.

The desired compound (I) thus obtained can be purified by conventional methods (e.g., chromatography, recrystallization, etc.).

The compound (XIII) in above Route 2 (Scheme 9) can also be prepared by the following reaction.

Route 4 ##STR25## wherein each symbol is as defined above.

The compound (XIII) can be prepared by reacting the compound (XV) with the compound (XIV) in the absence of a solvent or in an appropriate solvent.

The amount of the compound (XIV) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XV).

Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -30° C. to 150° C., preferably -10° C. to 120° C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.

Alternatively, the compound (I) of the present invention can be prepared by the following route.

Route 5 ##STR26## wherein each symbol is as defined above.

The compound (XVII) can be prepared by reacting the compound (XVI) with the compound (III) in the presence of a base in the absence of a solvent or in an appropriate solvent.

The amount of the compound (III) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVI).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVI).

Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 200° C., preferably 0° C. to 180° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The compound (XVII) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Alternatively, the compound (XVII) can also be prepared by the following reaction.

Route 5 (continued) ##STR27## wherein each symbol is as defined above.

The compound (XVII) can be prepared by reacting the compound (XVIII) with the compound (VI) in the presence of a base in the absence of a solvent or in an appropriate solvent.

The amount of the compound (VI) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVIII).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVIII).

Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 200° C., preferably 0° C. to 180° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The compound (XVII) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 5 (continued) ##STR28## wherein each symbol is as defined above.

The compound (XIX) can be prepared by reacting the compound (XVII) with hydroxylamine or a salt thereof (e.g., hydrochloric acid salt, sulfuric acid salt, etc.) in the presence or absence of a base in the absence of a solvent or in an appropriate solvent.

The amount of the hydroxylamine to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVII).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVII).

Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), water, etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -30° C. to 150° C., preferably -10° C. to 100° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The compound (XIX) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 5 (continued) ##STR29## wherein each symbol is as defined above.

The compound (XX) can be prepared by reacting the compound (XIX) with a halogenating agent in the absence of a solvent or in an appropriate solvent.

Examples of the halogenating agent include halogen (e.g., chlorine, bromine, etc.), N-halosuccinimide (e.g., N-bromosuccinimide, N-chlorosuccinimide, etc.), etc. The amount of the halogenating agent to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XIX).

Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, etc.), ethers (e.g., diethyl ether, dioxane, tetrahydrofuran (THF), etc.), etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -30° C. to 150° C., preferably -10° C. to 120° C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.

The compound (XX) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 5 (continued) ##STR30## wherein each symbol is as defined above.

The compound (Ib) of the present invention can be prepared by reacting the compound (XX) with the compound (XII) in the presence or absence of a base in the absence of a solvent or in an appropriate solvent.

The amount of the compound (XII) to be used is 1 mol or more, preferably 1 to 6 mol per mol of the compound (XX).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XX).

Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), etc. These solvents can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 200° C., preferably 0° C. to 180° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The compound (Ib) can be purified by conventional methods (e.g., chromatography, recrystallization, etc.). When the compound (Ib) is used in the next step, it can be used as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).

Route 5 (continued) ##STR31## wherein each symbol is as defined above.

The compound (I) of the present invention can be prepared by reacting the compound (Ib) with the compound (XXII) in the presence of a base in the absence of a solvent or in an appropriate solvent.

The amount of the compound (XXII) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (Ib).

Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (Ib).

Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvent can be used alone or in combination thereof.

The reaction temperature is normally -10° C. to 200° C., preferably 0° C. to 180° C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.

The desired compound (I) thus obtained can be purified by conventional methods (e.g., chromatography, recrystallization, etc.).

The compounds of the formula (I) of the present invention show a strong fungicidal activity against a wide variety of phytopathogenic fungi on crop plants (e.g., rice, wheat, barley, rye, corn, common millet, millet, buckwheat, soybean, redbean, peanut, etc.), fruit trees (e.g., citrus fruits, grape, apple, pear, peach, etc.), vegetables (e.g., cucumber, eggplant, tomato, pumpkin, kidney bean, etc.), etc. They also show fungicidal activity against phytopathogenic fungi in soil. Examples of the phytopathogenic fungi on which the compounds of the formula (I) of the present invention exert their fungicidal activity are Pyricularia oryzae, Rhizoctonia solani, Erysiphe graminis, Sphaerotheca fuliginea, Erysiphe cichoracearum, Phytophthora infestans, Pseudoperonospora cubensis, Peronospora manshurica, Plasmopara viticola, Botrytis cinerea of vegetables, grape, etc., Pythium aphanidermatum, Sclerotinia sclerotiorum of buckwheat, soybean, colza, etc., Corticium rolfsii of soybean, redbean, potato, peanut, etc., Pseudocercosporella herpotrichoides, etc. Therefore, the compounds (I) of the present invention are useful as agricultural fungicides.

Application of the compounds (I) of the present invention may be made to plants by any conventional procedure such as atomizing, scattering or spreading. Application may also be made through treatment of seeds of plants, soil where plants grow, paddy field for seedling or water for perfusion with the compounds (I). Application may be performed before and/or after the infection with phytopathogenic fungi on plants.

For the practical usage, the compounds (I) may be applied as such or in a formulation form suitable for agricultural fungicides such as solutions, wettable powders, emulsions, suspensions, concentrated liquid preparations, tablets, granules, aerosols, powders, pastes, dusts, etc. Such formulation form can be prepared in a conventional manner by mixing at least one of the compounds (I) with an appropriate solid or liquid carrier(s) and, if necessary, an appropriate adjuvant(s) (e.g., surfactants, spreaders, dispersants, stabilizers, etc.) for improving the dispersibility and other properties of the active ingredient.

Examples of the solid carriers or diluents include botanical materials (e.g., flour, tobacco stalk powder, soybean powder, walnut-shell powder, vegetable powder, saw dust, bran, bark powder, cellulose powder, vegetable extract residue, etc.), fibrous materials (e.g., paper, corrugated cardboard, old rags, etc.), artificial plastic powders, clays (e.g., kaolin, bentonire, fuller's earth, etc.), talc, other inorganic materials (e.g., pyrophyllite, sericite, pumice, sulfur powder, active carbon, etc.), chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.), etc.

Examples of the liquid carriers or diluents include water, alcohols (e.g., methanol, ethanol, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), ethers (e.g., diethyl ether, dioxane, cellosolve, tetrahydrofuran, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, methylnaphthalene, etc.), aliphatic hydrocarbons (e.g., gasoline, kerosene, lamp oil, etc.), esters, nitriles, acid amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenated hydrocarbons (e.g., dichloroethane, carbon tetrachloride, etc.), etc.

Examples of the surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters, etc.

Examples of the spreaders or dispersants include casein, gelatin, starch powder, carboxymethyl cellulose, gum arabic, alginic acid, lignin, bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc.

Examples of the stabilizers include PAP (a mixture of isopropylphosphate), tricresyl phosphate (TCP), tolu oil, epoxidized oil, surfactants, fatty acids and their esters, etc.

The composition of the present invention may contain other fungicides, insecticides, herbicides, fertilizers, etc., in addition to the above components.

When the compounds (I) are used as fungicidal compositions, each of such compositions contains at least one of the compounds (I) in a concentration of normally 0.1 to 95% by weight, preferably 2.0 to 80% by weight. These compositions can be used as such or in a diluted form. The concentration to be used depends upon a particular purpose, subject and plant to be treated, and it is generally in the range of about 1 to 50,000 ppm, preferably about 100 to 5,000 ppm. The amount of the compound (I) to be used is generally about 1.0 g to 5 kg/hectare, preferably about 2 g to 100 g/hectare.

Further, the compounds (I) of the present invention have excellent herbicidal activity against gramineous and broad-leaved weeds such as Digitaria ciliaris, Setaria viridis, Echinochloa crus-galli, Amaranthus lividus, Chenopodium album, Cyperus microiria, Mollugo stricta, Stellaria neglecta, Sagina japonica, Stellaria Alsine GRIMM var. undulata, Capsella bursa-pastoris, Alopecurus aequalis SOBOL var. amurensis, Poa annua, Polygonum longisetum, Polygonum lapathifolium, Trigonotis peduncularis, upland weeds such as Gnaphalium affine, paddy weeds such as Echinochloa oryzicola, Monochoria vaginalis, Cyperus difformis, Rotala indica, Dopatrium junceum, etc.

Further, the compounds (I) also have growth regulating activity (e.g., growth inhibiting activity) against gramineous and broad-leaved weeds, particularly lawns and balk weeds, and can inhibit the growth of grasses in paddy balks or lawns of golf courses for a long term.

The compounds (I) in certain amounts (e.g., 1 to 40 g/a) cause no or little damage to useful plants such as corn, sugarcane, sorghum, rice, wheat, barley, rye, soybean, peanut, cotton, etc. Even when the damage is caused, the damage is so slight that the damaged plants can readily recovered. Therefore, the compounds (I) can be used as selective or nonselective herbicides or growth regulating compositions (e.g., growth inhibiting compositions, compositions for reducing cutting frequency, and compositions for making felling easy, etc.) in arables such as plowed fields, paddy fields, fruit gardens, tea gardens, mulberry fields, arable lands not being used, pastures, and untillable lands such as railroads, roads, lawns, factory sites, riverbeds, housing lands, green tracts in parks, forests, created lands, vacant lands, etc.

The compounds (I) are harmless to humans, domestic animals and birds, and the toxicity to fishes is extremely low. Therefore the herbicides and growth regulating compositions are safe and the residual toxicity does not become a problem.

The compounds (I) can be used as herbicides or growth regulating compositions in various manners depending on the purpose, subject plants, term for use, etc. In general, treatment of soil or foliage application are preferred for the use as herbicides and foliage application is preferred for the use as growth regulating compositions. Each of such herbicidal compositions and growth regulating compositions contains at least one of the compounds (I) in a concentration of normally 0.1 to 95% by weight, preferably 2 to 80% by weight. These compositions can be used as such or in a diluted form. The concentration to be used depends upon a particular purpose, subject and plant to be treated, and it is generally in the range of about 1 to 50,000 ppm, preferably about 100 to 5,000 ppm. The amount of the compounds (I) to be used is generally about 10 g to 5 kg/hectare, preferably about 100 g to 1,000 g/hectare.

When the compounds (I) are used as herbicides or growth regulating compositions, the compounds (I) are used as such or in a formulation form such as powders, wettable powders, emulsions, etc., prepared by mixing various carriers depending on the sites where the compounds are applied. The carriers may be solid, liquid or combinations thereof. Examples of the solid carriers include clays, talc, diatomaceous earth, bentonite, etc. Examples of the liquid carriers include water, alcohols (e.g., methanol, ethanol, etc.), acetone, benzene, toluene, xylene, solvent naphtha, cyclohexane, etc. In addition, agriculturally acceptable emulsifying agents, stabilizers, dispersants, suspending agents, spreaders, penetrating agents, wetting agents, etc., can be formulated.

To increase the activity or obtain additive or synergistic action, the herbicides can be used in combination with other herbicides such as diuron, MCP, CNP, IPC, asulam, alachlor, trifluralin, etc. The herbicides or the growth regulating compositions of the present invention can also be used as a mixture with insecticides, fungicides, fertilizers, soil treating (improving) agents, etc.

Further, the benzaldehyde oxime derivatives of the present invention also have strong fungicidal activity against pathogenic fungi such as Candida, Aspergillus, Trichophyton, etc., and can be used as antifungal agents for treating such infectious diseases.

As described hereinabove, according to the present invention, there are provided novel benzaldehyde oxime derivatives, processes for producing them, and fungicidal, herbicidal and growth regulating compositions containing them as active ingredients.

The following examples and experiments further illustrate the present invention in detail, but are not to be construed to limit the scope thereof.

Example 1

Synthesis of 2-(2,4-dichlorobenzyloxy)benzoic acid

Dimethylformamide (DMF)(100 ml), potassium carbonate (17.97 g) and 2,4-dichlorobenzyl chloride (21.50 g) were added to methyl salicylate (15.22 g), and the mixture was stirred at room temperature overnight. Ethyl acetate (1000 ml) was added to the reaction mixture, and the resulting mixture was washed with brine (700 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give crude methyl 2-(2,4-dichlorobenzyloxy)benzoate. Methanol (100 ml), THF (100 ml), water (20 ml) and 85% potassium hydroxide (7.92 g) were added to the crude product thus obtained, and the mixture was stirred at 60° C. for 2 hours. After completion of the reaction, the mixture was concentrated under reduced pressure. Water (300 ml) was added to the residue, and the pH of the mixture was adjusted to not more than 2, and the resulting crystals were separated by filtration, dried to give 2-(2,4-dichlorobenzyloxy)benzoic acid (29.30 g) as colorless crystals.

Example 2

Synthesis of 2-(2,4-dichlorobenzyloxy)-N-methoxybenzamide

Dry dichloroethane (80 ml), thionyl chloride (3.16 ml) and DMF (0.2 ml) were added to 2-(2,4-dichlorobenzyloxy)benzoic acid (11.89 g), and the mixture was stirred under reflux for 1 hour. After completion of the reaction, the mixture was concentrated under reduced pressure, the residue was dissolved in dry methylene chloride (80 ml), the solution was added dropwise to a mixture of methoxyamine hydrochloride (6.68 g), pyridine (9.49 g) and methylene chloride (40 ml) under ice-cooling over 15 minutes, and the resulting mixture was stirred at room temperature for 1 hour. To the reaction mixture was added 1N hydrochloric acid (300 ml), and the resulting mixture was extracted with methylene chloride (150 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude crystals were recrystallized from ethyl acetate/n-hexane to give 2-(2,4-dichlorobenzyloxy)-N-methoxybenzamide (10.81 g) as colorless crystals. mp 100°-101.5° C.

Example 3

Synthesis of α-chloro-2-(2,4-dichlorobenzyloxy)benzaldehyde O-methyloxime

2-(2,4-Dichlorobenzyloxy)-N-methoxybenzamide (10.44 g) was dissolved in dry methylene chloride (100 ml), phosphorus pentachloride (6.66 g) was added under ice-cooling over about 3 minutes to the solution, and the mixture was stirred at 0° C. for 1 hour. After completion of the reaction, a saturated aqueous solution of sodium bicarbonate (150 ml) was added slowly, and the mixture was extracted with methylene chloride (150 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography to give α-chloro-2-(2,4-dichlorobenzyloxy)benzaldehyde O-methyloxime (9.52 g) as crystals. A part of the crystals was recrystallized from ethyl acetate/n-hexane to give colorless crystals. mp 91°-92° C.

Example 4

Synthesis of 2-(2,4-dichlorobenzyloxy)-α-(1-imidazolyl)benzaldehyde O-methyloxime (Compound 31)

Imidazole (2.04 g) was dissolved in DMF (30 ml), and 60% sodium hydride (1.20 g) was added. The mixture was stirred at room temperature for 10 minutes, then α-chloro-2-(2,4-dichlorobenzyloxy)benzaldehyde O-methyloxime (5.17 g) was added, and the mixture was stirred at 120° C. for 2 hours. After completion of the reaction, ether (200 ml) was added, and the mixture was washed with brine (200 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography and recrystallized from ethyl acetate/n-hexane to give 2-(2,4-dichlorobenzyloxy)-α-(1-imidazolyl)benzaldehyde O-methyloxime (2.74 g) as colorless crystals. mp. 122°-123° C.

Example 5

Synthesis of 2-(4-chlorobenzylthio)-α-(1-imidazolyl)benzaldehyde O-ethyloxime (Compound No. 155)

DMF (3 ml) and imidazole (0.41 g) were added to α-chloro-2-(4-chlorobenzylthio)benzaldehyde O-ethyloxime (0.68 g), and the mixture was stirred at 170° C. for 21 hours. After completion of the reaction, ether (100 ml) was added, and the mixture was washed with brine (80 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography and recrystallized from ethyl acetate/n-hexane to give 2-(4-chlorobenzylthio)-α-(1-imidazolyl)benzaldehyde O-ethyloxime (0.11 g) as colorless crystals. mp. 96.5°-97.5° C.

Example 6

Synthesis of 2-hydroxy-α-(1-imidazolyl)benzaldehyde O-methyloxime

Dry anisole (6 ml) and aluminium chloride (0.59 g) were added to 2-(2,4-dichlorobenzyloxy)-α-(1-imidazolyl)benzaldehyde O-methyloxime (0.75 g), and the mixture was stirred under ice-cooling for 2 hours. After completion of the reaction, a half-saturated aqueous solution of sodium bicarbonate (100 ml) was added slowly, and the mixture was extracted with ether (50 ml) and ethyl acetate (50 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography and recrystallized from ethyl acetate/n-hexane to give 2-hydroxy-α-(1-imidazolyl)benzaldehyde O-methyloxime (0.34 g) as colorless crystals. mp. 103.5°-104.5° C.

Example 7

Synthesis of α-(1-imidazolyl)-2-(4-methylbenzyloxy)benzaldehyde O-methyloxime (Compound 3)

DMF (3 ml), potassium carbonate (0.22 g) and 4-methylbenzyl chloride (0.20 g) were added to 2-hydroxy-α-(1-imidazolyl)benzaldehyde O-methyloxime (0.26 g), and the mixture was stirred at room temperature overnight. After completion of the reaction, ether (100 ml) was added, and the mixture was washed with brine (80 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography and recrystallized from ethyl acetate/n-hexane to give α-(1-imidazolyl)-2-(4-methylbenzyloxy)benzaldehyde O-methyloxime (0.22 g) as colorless crystals. mp. 70.5°-72.0° C.

Example 8

Synthesis of 2-(4-chlorobenzyloxy)-α-(1-imidazolyl)benzaldehyde O-methyloxime (Compound 9)

Thionyl chloride (0.16 ml) was added to a suspension of imidazole (0.63 g) and methylene chloride (6 ml) under ice-cooling, and the mixture was stirred under ice-cooling for 30 minutes. Then 2-(4-chlorobenzyloxy)-N-methoxybenzamide (0.44 g) was added, and the mixture was stirred under reflux for 2 hours. After completion of the reaction, water (100 ml) was added, and the mixture was extracted with methylene chloride (50 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography to give 2-(4-chlorobenzyloxy)-α-(1-imidazolyl)benzaldehyde O-methyloxime (0.01 g) as colorless crystals. mp. 92.5°-93.5° C.

Example 9

Synthesis of 2-(4-chlorobenzyloxy)benzaldehyde oxime

Potassium carbonate (33.17 g) and DMF (180 ml) were added to salicylaldehyde (24.42 g), and the mixture was stirred at room temperature for 10 minutes. Then a mixture of 4-chlorobenzyl chloride (33.82 g) and DMF (20 ml) was added at room temperature over 15 minutes, and the mixture was stirred at 60° C. for 3 hours. After completion of the reaction, ether (500 ml) was added, and the mixture was washed with water (400 ml) three times, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give crude 2-(4-chlorobenzyloxy)benzaldehyde. The ethanol (200 ml) and hydroxylamine hydrochloride (27.80 g) was added to the crude product, and the mixture was stirred at 80° C. overnight. After completion of the reaction, water (400 ml) was added, and the mixture was extracted with methylene chloride (200 ml) three times, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was recrystallized from ethyl acetate/n-hexane to give 2-(4-chlorobenzyloxy)benzaldehyde oxime (32.06 g) as colorless crystals. mp. 122.5°-123.5° C.

Example 10

Synthesis of 2-(4-chlorobenzyloxy)-α-(1-imidazolyl)benzaldehyde oxime

2-(4-Chlorobenzyloxy)benzaldehyde oxime (26.17 g) was dissolved in ether (200 ml) and methylene chloride (50 ml), and chlorine (6.0 ml) was introduced at -10° C. or below, and then the temperature was raised from -10° C. to room temperature over 2 hours. After completion of the reaction, the mixture was concentrated under reduced pressure to give crude α-chloro-2-(4-chlorobenzyloxy)benzaldehyde oxime. The resulting crude product was dissolved in acetonitrile (150 ml), a mixture of imidazole (17.02 g) and acetonitrile (100 ml) was added at room temperature over 15 minutes, and then the resulting mixture was stirred at 65 to 70° C. for 2 hours. After completion of the reaction, water and methylene chloride were added. The resulting crystals were separated by filtration to give 2-(4-chlorobenzyloxy)-α-(1-imidazolyl)benzaldehyde oxime (11.05 g) as colorless crystals. mp. 196°-197° C.

Example 11

Synthesis of 2-(4-chlorobenzyloxy)-α-(1-imidazolyl)benzaldehyde O-benzyloxime

Potassium carbonate (0.21 g), benzyl chloride (0.15 g) and DMF (2 ml) were added to 2-(4-chlorobenzyloxy)-α-(1-imidazolyl)benzaldehyde oxime (0.33 g), and the mixture was stirred at 60° C. for 2 hours. After completion of the reaction, ether (100 ml) was added, and the mixture was extracted with brine (80 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography to give 2-(4-chlorobenzyloxy)-α-(1-imidazolyl)benzaldehyde O-benzyloxime (0.38 g) as colorless crystals. mp. 94°-95.5° C.

Example 12

Synthesis of α-(1-imidazolyl)-2-(1-phenylpropyloxy)benzaldehyde O-methyloxime

Triphenylphosphine (1.05 g), 1-phenylpropyl alcohol (0.54 g) and THF (20 ml) were added to 2-hydroxy-α-(1-imidazolyl)benzaldehyde O-methyloxime (0.43 g), and diethyl azodicarboxylate (0.70 g) was added under ice-cooling over 10 minutes. Then the mixture was stirred at room temperature for 2 hours. After completion of the reaction, ether (100 ml) was added, the mixture was washed with water (80 ml) twice, and the ether layer was concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography to give α-(1-imidazolyl)-2-(1-phenylpropyloxy)benzaldehyde O-methyloxime (0.63 g) as a colorless oil.

Example 13

According the same manner as that described above, the compounds in the following tables (Compound Nos. 1 to 1130) were prepared.

The physical properties of the representative compounds obtained are in Tables 1 to 156. In the tables, the physical properties of the compounds obtained in Examples 4, 5, 7 and 8 are also listed. In the tables, Me means methyl, Et means ethyl, n-Pr means n-propyl, i-Pr means isopropyl, i-Bu means isobutyl, t-Bu means t-butyl, Ph means phenyl, and Bn means benzyl.

The ¹ H-NMR values were determined on 270 MHz and are indicated in terms of δ values (ppm) using tetramethylsilane in CDCl₃ as the internal standard. The spin coupling constants (J) are indicated in terms of Hz. In the NMR data, s means a singlet, d means a doublet, t means a triplet, q means a quartet, quint means a quintet, sext means a sextet, sept means a septet, and m means a multiplet.

                                      TABLE 1                                      __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________         ##STR32##        Me  H   O  CH                                                                                       ##STR33##                            2                                                                                  ##STR34##        Me  H   O  CH                                             3                                                                                  ##STR35##        Me  H   O  CH 70.5-72                                                                               ##STR36##                            4                                                                                  ##STR37##        Me  H   O  CH                                             5                                                                                  ##STR38##        Me  H   O  CH                                             6                                                                                  ##STR39##        Me  H   O  CH                                             7                                                                                  ##STR40##        Me  H   O  CH 91.5-92.5                                                                             ##STR41##                            __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________      8                                                                                 ##STR42##        Me  H   O  CH                                              9                                                                                 ##STR43##        Me  H   O  CH 92.5-93.5                                                                             ##STR44##                            10                                                                                 ##STR45##        Me  H   O  CH                                             11                                                                                 ##STR46##        Me  H   O  CH                                             12                                                                                 ##STR47##        Me  H   O  CH                                             13                                                                                 ##STR48##        Me  H   O  CH                                             14                                                                                 ##STR49##        Me  H   O  CH                                             15                                                                                 ##STR50##        Me  H   O  CH                                                                                       ##STR51##                            __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     16                                                                                 ##STR52##        Me  H   O  CH                                             17                                                                                 ##STR53##        Me  H   O  CH                                             18                                                                                 ##STR54##        Me  H   O  CH                                             19                                                                                 ##STR55##        Me  H   O  CH                                             20                                                                                 ##STR56##        Me  H   O  CH                                             21                                                                                 ##STR57##        Me  H   O  CH                                             22                                                                                 ##STR58##        Me  H   O  CH                                             __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     23                                                                                 ##STR59##        Me  H   O  CH                                             24                                                                                 ##STR60##        Me  H   O  CH                                             25                                                                                 ##STR61##        Me  H   O  CH                                             26                                                                                 ##STR62##        Me  H   O  CH                                                                                       ##STR63##                            27                                                                                 ##STR64##        Me  H   O  CH                                             28                                                                                 ##STR65##        Me  H   O  CH                                             29                                                                                 ##STR66##        Me  H   O  CH                                             30                                                                                 ##STR67##        Me  H   O  CH                                             __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     31                                                                                 ##STR68##        Me  H   O  CH 122-123                                                                               ##STR69##                            32                                                                                 ##STR70##        Me  H   O  CH 110.5-111.5                                                                           ##STR71##                            33                                                                                 ##STR72##        Me  H   O  CH                                             34                                                                                 ##STR73##        Me  H   O  CH                                             35                                                                                 ##STR74##        Me  H   O  CH                                                                                       ##STR75##                            36                                                                                 ##STR76##        Me  H   O  CH                                             37                                                                                 ##STR77##        Me  H   O  CH                                             __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     38                                                                                 ##STR78##        Me  H   O  CH                                             39                                                                                 ##STR79##        Me  H   O  CH                                             40                                                                                 ##STR80##        Me  H   O  CH                                             41                                                                                 ##STR81##        Me  H   O  CH                                             42                                                                                 ##STR82##        Me  H   O  CH                                             43                                                                                 ##STR83##        Me  H   O  CH                                             44                                                                                 ##STR84##        Me  H   O  CH                                             45                                                                                 ##STR85##        Me  H   O  CH                                             __________________________________________________________________________

                                      TABLE 7                                      __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     46                                                                                 ##STR86##        Me  H   O  CH                                             47                                                                                 ##STR87##        Me  H   O  CH                                             48                                                                                 ##STR88##        Me  H   O  CH                                             49                                                                                 ##STR89##        Me  H   O  CH 118-119                                                                               ##STR90##                            50                                                                                 ##STR91##        Me  H   O  CH                                             51                                                                                 ##STR92##        Me  H   O  CH 128-129                                                                               ##STR93##                            52 PhOCH.sub.2 CH.sub.2                                                                             Me  H   O  CH                                                                                       ##STR94##                            __________________________________________________________________________

                                      TABLE 8                                      __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     53 MeOCOCH.sub.2     Me  H   O  CH       3.72(3H, s), 4.05(3H, s),                                                      4.50(2H, s), 6.78-                                                             7.53(6H, m), 8.03(1H, s)              54 PhCOCH.sub.2      Me  H   O  CH       4.04(3H, s), 5.15(2H, s),                                                      6.79-7.86(11H, m),                                                             8.04(1H, s)                           55                                                                                 ##STR95##        Me  H   S  CH                                                                                       ##STR96##                            56                                                                                 ##STR97##        Me  H   S  CH                                             57                                                                                 ##STR98##        Me  H   S  CH                                             58                                                                                 ##STR99##        Me  H   S  CH 74.5-75.5                                   59                                                                                 ##STR100##       Me  H   S  CH                                             60                                                                                 ##STR101##       Me  H   S  CH                                             __________________________________________________________________________

                                      TABLE 9                                      __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     61                                                                                 ##STR102##       Me  H   S  CH                                             62                                                                                 ##STR103##       Me  H   O  N  91.5-92.5                                   63                                                                                 ##STR104##       Me  H   O  N  124-125                                     64                                                                                 ##STR105##       Me  H   O  N                                              65                                                                                 ##STR106##       Me  H   O  N                                                                                        ##STR107##                           66                                                                                 ##STR108##       Me  H   O  N  130-131                                                                               ##STR109##                           67                                                                                 ##STR110##       Me  H   O  CH                                             68                                                                                 ##STR111##       Me  H   O  CH                                                                                       ##STR112##                           __________________________________________________________________________

                                      TABLE 10                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     69                                                                                 ##STR113##       Me  H   O  CH                                             70                                                                                 ##STR114##       Me  H   O  CH 75.5-76.5                                                                             ##STR115##                           71                                                                                 ##STR116##       Me  H   O  CH 147-148                                                                               ##STR117##                           72                                                                                 ##STR118##       Me  H   O  CH 76-77                                                                                 ##STR119##                           73                                                                                 ##STR120##       Me  H   O  CH                                             74                                                                                 ##STR121##       Me  H   O  CH                                             75                                                                                 ##STR122##       Me  H   O  CH                                             __________________________________________________________________________

                                      TABLE 11                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     76                                                                                 ##STR123##       Me  H   O  CH 42-49                                                                                 ##STR124##                           77                                                                                 ##STR125##       Me  H   O  CH                                             78                                                                                 ##STR126##       Me  H   O  CH                                             79                                                                                 ##STR127##       Me  H   O  CH 80-81                                                                                 ##STR128##                           80                                                                                 ##STR129##       Me  H   O  CH                                             81                                                                                 ##STR130##       Me  H   O  CH                                                                                       ##STR131##                           82                                                                                 ##STR132##       Me  H   O  CH                                                                                       ##STR133##                           __________________________________________________________________________

                                      TABLE 12                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     83                                                                                 ##STR134##       Me  H   O  CH 94.5-95.5                                                                             ##STR135##                           84                                                                                 ##STR136##       Me  H   O  CH                                             85                                                                                 ##STR137##       Me  H   O  CH                                             86                                                                                 ##STR138##       Me  H   O  CH                                                                                       ##STR139##                           87                                                                                 ##STR140##       Me  H   O  CH                                                                                       ##STR141##                           88                                                                                 ##STR142##       Me  H   O  CH                                             89                                                                                 ##STR143##       Me  H   O  CH                                                                                       ##STR144##                           90                                                                                 ##STR145##       Me  H   O  CH                                             __________________________________________________________________________

                                      TABLE 13                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     91                                                                                 ##STR146##       Me  H   O  CH                                             92                                                                                 ##STR147##       Me  H   O  CH                                                                                       ##STR148##                           93                                                                                 ##STR149##       Me  H   O  CH                                             94                                                                                 ##STR150##       Me  H   O  CH                                             95                                                                                 ##STR151##       Me  H   O  CH                                             96                                                                                 ##STR152##       Me  H   O  CH                                                                                       ##STR153##                           97                                                                                 ##STR154##       Me  H   O  CH                                             __________________________________________________________________________

                                      TABLE 14                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     98                                                                                 ##STR155##       Me  H   O  CH                                                                                       ##STR156##                           99                                                                                 ##STR157##       Me  H   O  CH                                             100                                                                                ##STR158##       Me  H   O  CH                                             __________________________________________________________________________

                                      TABLE 15                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     101                                                                                ##STR159##       Et  H   O  CH                                                                                       ##STR160##                           102                                                                                ##STR161##       Et  H   O  CH                                             103                                                                                ##STR162##       Et  H   O  CH 80-82                                                                                 ##STR163##                           104                                                                                ##STR164##       Et  H   O  CH                                                                                       ##STR165##                           105                                                                                ##STR166##       Et  H   O  CH                                             106                                                                                ##STR167##       Et  H   O  CH 77-79                                                                                 ##STR168##                           107                                                                                ##STR169##       Et  H   O  CH 67-70                                                                                 ##STR170##                           __________________________________________________________________________

                                      TABLE 16                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     108                                                                                ##STR171##       Et  H   O  CH 73.5-75                                                                               ##STR172##                           109                                                                                ##STR173##       Et  H   O  CH 99.5-100.5                                                                            ##STR174##                           110                                                                                ##STR175##       Et  H   O  CH                                                                                       ##STR176##                           111                                                                                ##STR177##       Et  H   O  CH                                             112                                                                                ##STR178##       Et  H   O  CH                                             113                                                                                ##STR179##       Et  H   O  CH                                             114                                                                                ##STR180##       Et  H   O  CH                                             115                                                                                ##STR181##       Et  H   O  CH                                                                                       ##STR182##                           __________________________________________________________________________

                                      TABLE 17                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     116                                                                                ##STR183##       Et  H   O  CH                                             117                                                                                ##STR184##       Et  H   O  CH                                             118                                                                                ##STR185##       Et  H   O  CH                                                                                       ##STR186##                           119                                                                                ##STR187##       Et  H   O  CH                                             120                                                                                ##STR188##       Et  H   O  CH 104.5-106.5                                                                           ##STR189##                           121                                                                                ##STR190##       Et  H   O  CH                                             122                                                                                ##STR191##       Et  H   O  CH                                             __________________________________________________________________________

                                      TABLE 18                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     123                                                                                ##STR192##       Et  H   O  CH                                             124                                                                                ##STR193##       Et  H   O  CH                                                                                       ##STR194##                           125                                                                                ##STR195##       Et  H   O  CH                                             126                                                                                ##STR196##       Et  H   O  CH                                                                                       ##STR197##                           127                                                                                ##STR198##       Et  H   O  CH 88.0-89.5                                   128                                                                                ##STR199##       Et  H   O  CH                                                                                       ##STR200##                           129                                                                                ##STR201##       Et  H   O  CH   72-73.5                                                                             ##STR202##                           130                                                                                ##STR203##       Et  H   O  CH                                             __________________________________________________________________________

                                      TABLE 19                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     131                                                                                ##STR204##       Et  H   O  CH 106.5-107.5                                                                           ##STR205##                           132                                                                                ##STR206##       Et  H   O  CH 97-98                                                                                 ##STR207##                           133                                                                                ##STR208##       Et  H   O  CH 113-114                                                                               ##STR209##                           134                                                                                ##STR210##       Et  H   O  CH                                             135                                                                                ##STR211##       Et  H   O  CH                                             136                                                                                ##STR212##       Et  H   O  CH                                             137                                                                                ##STR213##       Et  H   O  CH                                             __________________________________________________________________________

                                      TABLE 20                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     138                                                                                ##STR214##       Et  H   O  CH                                             139                                                                                ##STR215##       Et  H   O  CH                                             140                                                                                ##STR216##       Et  H   O  CH                                             141                                                                                ##STR217##       Et  H   O  CH                                             142                                                                                ##STR218##       Et  H   O  CH                                             143                                                                                ##STR219##       Et  H   O  CH                                             144                                                                                ##STR220##       Et  H   O  CH                                             145                                                                                ##STR221##       Et  H   O  CH                                             __________________________________________________________________________

                                      TABLE 21                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     146                                                                                ##STR222##       Et  H   O  CH                                             147                                                                                ##STR223##       Et  H   O  CH                                             148                                                                                ##STR224##       Et  H   O  CH                                             149                                                                                ##STR225##       Et  H   O  CH 84.5-85.5                                                                             ##STR226##                           150                                                                                ##STR227##       Et  H   O  CH                                             151                                                                                ##STR228##       Et  H   O  CH                                             152                                                                               PhOCH.sub.2 CH.sub.2                                                                             Et  H   O  CH                                                                                       ##STR229##                           __________________________________________________________________________

                                      TABLE 22                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     153                                                                                ##STR230##       Et  H   O  CH                                                                                       ##STR231##                           154                                                                               PhCOCH.sub.2      Et  H   O  CH                                             155                                                                                ##STR232##       Et  H   S  CH 96.5-97.5                                                                             ##STR233##                           156                                                                                ##STR234##       Et  H   S  CH                                             157                                                                                ##STR235##       Et  H   S  CH                                             158                                                                                ##STR236##       Et  H   S  CH                                             159                                                                                ##STR237##       Et  H   S  CH                                             160                                                                                ##STR238##       Et  H   S  CH                                             __________________________________________________________________________

                                      TABLE 23                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     161                                                                                ##STR239##       Et  H   O  CH                                                                                       ##STR240##                           162                                                                               PhO(CH.sub.2).sub.3                                                                              Et  H   O  CH                                             163                                                                                ##STR241##       Et  H   O  N                                              164                                                                                ##STR242##       Et  H   O  N                                              165                                                                                ##STR243##       Et  H   O  N                                                                                        ##STR244##                           166                                                                                ##STR245##       Et  H   O  N                                              167                                                                                ##STR246##       Et  H   O  CH                                             168                                                                                ##STR247##       Et  H   O  CH                                                                                       ##STR248##                           __________________________________________________________________________

                                      TABLE 24                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     169                                                                                ##STR249##       Et  H   O  CH                                             170                                                                                ##STR250##       Et  H   O  CH 65-66                                                                                 ##STR251##                           171                                                                                ##STR252##       Et  H   O  CH   131-132.5                                                                           ##STR253##                           172                                                                                ##STR254##       Et  H   O  CH 81-82                                                                                 ##STR255##                           173                                                                                ##STR256##       Et  H   O  CH                                             174                                                                                ##STR257##       Et  H   O  CH                                             175                                                                                ##STR258##       Et  H   O  CH                                             __________________________________________________________________________

                                      TABLE 25                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     176                                                                                ##STR259##       Et  H   O  CH                                             177                                                                                ##STR260##       Et  H   O  CH                                             178                                                                                ##STR261##       Et  H   O  CH                                                                                       ##STR262##                           179                                                                                ##STR263##       Et  H   O  CH                                                                                       ##STR264##                           180                                                                                ##STR265##       Et  H   O  CH                                             181                                                                                ##STR266##       Et  H   O  CH                                                                                       ##STR267##                           182                                                                                ##STR268##       Et  H   O  CH                                             __________________________________________________________________________

                                      TABLE 26                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     183                                                                                ##STR269##       Et  H   O  CH                                                                                       ##STR270##                           184                                                                                ##STR271##       Et  H   O  CH                                                                                       ##STR272##                           185                                                                                ##STR273##       Et  H   O  CH                                             186                                                                                ##STR274##       Et  H   O  CH 71-73                                                                                 ##STR275##                           187                                                                                ##STR276##       Et  H   O  CH                                                                                       ##STR277##                           188                                                                                ##STR278##       Et  H   O  CH                                             189                                                                                ##STR279##       Et  H   O  CH                                                                                       ##STR280##                           190                                                                                ##STR281##       Et  H   O  CH                                             __________________________________________________________________________

                                      TABLE 27                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     191                                                                                ##STR282##       Et        H   O  CH                                                                                 ##STR283##                                                                         ##STR284##                       192                                                                                ##STR285##       Et        H   O  CH                                                                                     ##STR286##                       193                                                                                ##STR287##       Et        H   O  CH                                       194                                                                                ##STR288##       Et        H   O  CH                                       195                                                                                ##STR289##       Et        H   O  CH                                       196                                                                                ##STR290##       Et        H   O  CH                                                                                     ##STR291##                       197                                                                                ##STR292##       Et        H   O  CH                                       __________________________________________________________________________

                                      TABLE 28                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     198                                                                                ##STR293##       Et        H   O  CH                                       199                                                                                ##STR294##       Et        H   O  CH                                                                                     ##STR295##                       200                                                                                ##STR296##       Et        H   O  CH                                       __________________________________________________________________________

                                      TABLE 29                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     201                                                                                ##STR297##       Allyl     H   O  CH                                       202                                                                                ##STR298##       Allyl     H   O  CH                                       203                                                                                ##STR299##       Allyl     H   O  CH                                                                                     ##STR300##                       204                                                                                ##STR301##       Allyl     H   O  CH                                       205                                                                                ##STR302##       Allyl     H   O  CH                                       206                                                                                ##STR303##       Allyl     H   O  CH                                       207                                                                                ##STR304##       Allyl     H   O  CH                                                                                     ##STR305##                       __________________________________________________________________________

                                      TABLE 30                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     208                                                                                ##STR306##       Allyl     H   O  CH                                       209                                                                                ##STR307##       Allyl     H   O  CH                                                                                 ##STR308##                                                                         ##STR309##                       210                                                                                ##STR310##       Allyl     H   O  CH                                       211                                                                                ##STR311##       Allyl     H   O  CH                                       212                                                                                ##STR312##       Allyl     H   O  CH                                       213                                                                                ##STR313##       Allyl     H   O  CH                                       214                                                                                ##STR314##       Allyl     H   O  CH                                       215                                                                                ##STR315##       Allyl     H   O  CH                                       __________________________________________________________________________

                                      TABLE 31                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     216                                                                                ##STR316##       Allyl     H   O  CH                                       217                                                                                ##STR317##       Allyl     H   O  CH                                       218                                                                                ##STR318##       Allyl     H   O  CH                                       219                                                                                ##STR319##       Allyl     H   O  CH                                       220                                                                                ##STR320##       Allyl     H   O  CH                                       221                                                                                ##STR321##       Allyl     H   O  CH                                       222                                                                                ##STR322##       Allyl     H   O  CH                                       __________________________________________________________________________

                                      TABLE 32                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     223                                                                                ##STR323##       Allyl     H   O  CH                                       224                                                                                ##STR324##       Allyl     H   O  CH                                       225                                                                                ##STR325##       Allyl     H   O  CH                                       226                                                                                ##STR326##       Allyl     H   O  CH                                                                                     ##STR327##                       227                                                                                ##STR328##       Allyl     H   O  CH                                       228                                                                                ##STR329##       Allyl     H   O  CH                                       229                                                                                ##STR330##       Allyl     H   O  CH                                       230                                                                                ##STR331##       Allyl     H   O  CH                                       __________________________________________________________________________

                                      TABLE 33                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     231                                                                                ##STR332##       Allyl     H   O  CH                                       232                                                                                ##STR333##       Allyl     H   O  CH                                       233                                                                                ##STR334##       Allyl     H   O  CH  92.5-  93.5                                                                       4.72-4.75(2H, m), 4.88(2H,                                                     s), 5.25- 5.40(2H, m),                                                         5.98-6.12(1H, m), 6.85(1H,                                                     dd, J=8.6, 2.4), 6.94(1H, d,                                                   =8.5), 7.06-7.54(7H, m),                                                       7.96(1H, s)                       234                                                                                ##STR335##       Allyl     H   O  CH                                       235                                                                                ##STR336##       Allyl     H   O  CH                                       236                                                                                ##STR337##       Allyl     H   O  CH                                       237                                                                                ##STR338##       Allyl     H   O  CH                                       __________________________________________________________________________

                                      TABLE 34                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     238                                                                                ##STR339##       Allyl     H   O  CH                                       239                                                                                ##STR340##       Allyl     H   O  CH                                       240                                                                                ##STR341##       Allyl     H   O  CH                                       241                                                                                ##STR342##       Allyl     H   O  CH                                       242                                                                                ##STR343##       Allyl     H   O  CH                                       243                                                                                ##STR344##       Allyl     H   O  CH                                       244                                                                                ##STR345##       Allyl     H   O  CH                                       245                                                                                ##STR346##       Allyl     H   O  CH                                       __________________________________________________________________________

                                      TABLE 35                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     246                                                                                ##STR347##       Allyl     H   O  CH                                       247                                                                                ##STR348##       Allyl     H   O  CH                                       248                                                                                ##STR349##       Allyl     H   O  CH                                       249                                                                                ##STR350##       Allyl     H   O  CH                                       250                                                                                ##STR351##       Allyl     H   O  CH                                       251                                                                                ##STR352##       Allyl     H   O  CH                                       252                                                                               PhOCH.sub.2 CH.sub.2                                                                             Allyl     H   O  CH                                       __________________________________________________________________________

                                      TABLE 36                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     253                                                                                ##STR353##       Allyl     H   O  CH                                                                                 ##STR354##                                                                         ##STR355##                       254                                                                               PhCOCH.sub.2      Allyl     H   O  CH                                       255                                                                                ##STR356##       Allyl     H   S  CH                                       256                                                                                ##STR357##       Allyl     H   S  CH                                       257                                                                                ##STR358##       Allyl     H   S  CH                                       258                                                                                ##STR359##       Allyl     H   S  CH                                       259                                                                                ##STR360##       Allyl     H   S  CH                                       260                                                                                ##STR361##       Allyl     H   S  CH                                       __________________________________________________________________________

                                      TABLE 37                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     261                                                                                ##STR362##       Allyl     H   O  CH                                       262                                                                               PhO(CH.sub.2).sub.3                                                                              Allyl     H   O  CH                                       263                                                                                ##STR363##       Allyl     H   O  N                                        264                                                                                ##STR364##       Allyl     H   O  N                                        265                                                                                ##STR365##       Allyl     H   O  N                                        266                                                                                ##STR366##       Allyl     H   O  N                                        267                                                                                ##STR367##       Allyl     H   O  CH                                       __________________________________________________________________________

                                      TABLE 38                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     268                                                                                ##STR368##       Allyl     H   O  CH                                       269                                                                                ##STR369##       Allyl     H   O  CH                                       270                                                                                ##STR370##       Allyl     H   O  CH 57-58                                                                               ##STR371##                       271                                                                                ##STR372##       Allyl     H   O  CH                                       272                                                                                ##STR373##       Allyl     H   O  CH                                       273                                                                                ##STR374##       Allyl     H   O  CH                                       274                                                                                ##STR375##       Allyl     H   O  CH                                       275                                                                                ##STR376##       Allyl     H   O  CH                                       __________________________________________________________________________

                                      TABLE 39                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     276                                                                                ##STR377##       Allyl     H   O  CH                                       277                                                                                ##STR378##       Allyl     H   O  CH                                       278                                                                                ##STR379##       Allyl     H   O  CH                                       279                                                                                ##STR380##       Allyl     H   O  CH                                       280                                                                                ##STR381##       Allyl     H   O  CH                                       281                                                                                ##STR382##       Allyl     H   O  CH                                                                                     ##STR383##                       282                                                                                ##STR384##       Allyl     H   O  CH                                       __________________________________________________________________________

                                      TABLE 40                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     283                                                                                ##STR385##       Allyl                                                                              H   O  CH                                                                                       ##STR386##                           284                                                                                ##STR387##       Allyl                                                                              H   O  CH                                             285                                                                                ##STR388##       Allyl                                                                              H   O  CH                                             286                                                                                ##STR389##       Allyl                                                                              H   O  CH                                                                                       ##STR390##                           287                                                                                ##STR391##       Allyl                                                                              H   O  CH                                             288                                                                                ##STR392##       Allyl                                                                              H   O  CH                                             289                                                                                ##STR393##       Allyl                                                                              H   O  CH                                             290                                                                                ##STR394##       Allyl                                                                              H   O  CH                                             __________________________________________________________________________

                                      TABLE 41                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     291                                                                                ##STR395##       Allyl                                                                              H   O  CH                                             292                                                                                ##STR396##       Allyl                                                                              H   O  CH                                             293                                                                                ##STR397##       Allyl                                                                              H   O  CH                                             294                                                                                ##STR398##       Allyl                                                                              H   O  CH                                             295                                                                                ##STR399##       Allyl                                                                              H   O  CH                                             296                                                                                ##STR400##       Allyl                                                                              H   O  CH                                             297                                                                                ##STR401##       Allyl                                                                              H   O  CH                                             __________________________________________________________________________

                                      TABLE 42                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     298                                                                                ##STR402##       Allyl                                                                              H   O  CH                                                                                       ##STR403##                           299                                                                                ##STR404##       Allyl                                                                              H   O  CH                                             300                                                                                ##STR405##       Allyl                                                                              H   O  CH                                             __________________________________________________________________________

                                      TABLE 43                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     301                                                                                ##STR406##       i-Bu                                                                               H   O  CH                                             302                                                                                ##STR407##       i-Bu                                                                               H   O  CH                                             303                                                                                ##STR408##       i-Bu                                                                               H   O  CH 84-86                                                                                 ##STR409##                           304                                                                                ##STR410##       i-Bu                                                                               H   O  CH                                             305                                                                                ##STR411##       i-Bu                                                                               H   O  CH                                             306                                                                                ##STR412##       i-Bu                                                                               H   O  CH 73-74                                                                                 ##STR413##                           307                                                                                ##STR414##       i-Bu                                                                               H   O  CH                                                                                       ##STR415##                           __________________________________________________________________________

                                      TABLE 44                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     308                                                                                ##STR416##       i-Bu                                                                               H   O  CH                                             309                                                                                ##STR417##       i-Bu                                                                               H   O  CH 84-85                                                                                 ##STR418##                           310                                                                                ##STR419##       i-Bu                                                                               H   O  CH                                             311                                                                                ##STR420##       i-Bu                                                                               H   O  CH                                             312                                                                                ##STR421##       i-Bu                                                                               H   O  CH                                             313                                                                                ##STR422##       i-Bu                                                                               H   O  CH                                             314                                                                                ##STR423##       i-Bu                                                                               H   O  CH                                             315                                                                                ##STR424##       i-Bu                                                                               H   O  CH                                                                                       ##STR425##                           __________________________________________________________________________

                                      TABLE 45                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     316                                                                                ##STR426##       i-Bu                                                                               H   O  CH                                             317                                                                                ##STR427##       i-Bu                                                                               H   O  CH                                             318                                                                                ##STR428##       i-Bu                                                                               H   O  CH                                             319                                                                                ##STR429##       i-Bu                                                                               H   O  CH                                             320                                                                                ##STR430##       i-Bu                                                                               H   O  CH                                             321                                                                                ##STR431##       i-Bu                                                                               H   O  CH                                             322                                                                                ##STR432##       i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 46                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     323                                                                                ##STR433##       i-Bu                                                                               H   O  CH                                             324                                                                                ##STR434##       i-Bu                                                                               H   O  CH                                             325                                                                                ##STR435##       i-Bu                                                                               H   O  CH                                             326                                                                                ##STR436##       i-Bu                                                                               H   O  CH 81-82                                                                                 ##STR437##                           327                                                                                ##STR438##       i-Bu                                                                               H   O  CH                                             328                                                                                ##STR439##       i-Bu                                                                               H   O  CH                                             329                                                                                ##STR440##       i-Bu                                                                               H   O  CH                                             330                                                                                ##STR441##       i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 47                                     __________________________________________________________________________     No.                                                                               R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     331                                                                                ##STR442##       i-Bu                                                                               H   O  CH                                             332                                                                                ##STR443##       i-Bu                                                                               H   O  CH                                             333                                                                                ##STR444##       i-Bu                                                                               H   O  CH 95.5-96.5                                                                             ##STR445##                           334                                                                                ##STR446##       i-Bu                                                                               H   O  CH                                             335                                                                                ##STR447##       i-Bu                                                                               H   O  CH                                             336                                                                                ##STR448##       i-Bu                                                                               H   O  CH                                             337                                                                                ##STR449##       i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 48                                     __________________________________________________________________________     No.                                                                               R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     338                                                                                ##STR450##       i-Bu                                                                               H   O  CH                                             339                                                                                ##STR451##       i-Bu                                                                               H   O  CH                                             340                                                                                ##STR452##       i-Bu                                                                               H   O  CH                                             341                                                                                ##STR453##       i-Bu                                                                               H   O  CH                                             342                                                                                ##STR454##       i-Bu                                                                               H   O  CH                                             343                                                                                ##STR455##       i-Bu                                                                               H   O  CH                                             344                                                                                ##STR456##       i-Bu                                                                               H   O  CH                                             345                                                                                ##STR457##       i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 49                                     __________________________________________________________________________     No.                                                                               R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     346                                                                                ##STR458##       i-Bu                                                                               H   O  CH                                             347                                                                                ##STR459##       i-Bu                                                                               H   O  CH                                             348                                                                                ##STR460##       i-Bu                                                                               H   O  CH                                             349                                                                                ##STR461##       i-Bu                                                                               H   O  CH                                             350                                                                                ##STR462##       i-Bu                                                                               H   O  CH                                             351                                                                                ##STR463##       i-Bu                                                                               H   O  CH                                             352                                                                               PhOCH.sub.2 CH.sub.2                                                                             i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 50                                     __________________________________________________________________________     No.                                                                               R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     353                                                                                ##STR464##       i-Bu                                                                               H   O  CH                                             354                                                                               PhCOCH.sub.2      i-Bu                                                                               H   O  CH                                             355                                                                                ##STR465##       i-Bu                                                                               H   S  CH                                             356                                                                                ##STR466##       i-Bu                                                                               H   S  CH                                             357                                                                                ##STR467##       i-Bu                                                                               H   S  CH                                             358                                                                                ##STR468##       i-Bu                                                                               H   S  CH                                             359                                                                                ##STR469##       i-Bu                                                                               H   S  CH                                             360                                                                                ##STR470##       i-Bu                                                                               H   S  CH                                             __________________________________________________________________________

                                      TABLE 51                                     __________________________________________________________________________     No.                                                                               R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     361                                                                                ##STR471##       i-Bu                                                                               H   O  CH                                             362                                                                               PhO(CH.sub.2).sub.3                                                                              i-Bu                                                                               H   O  CH                                             363                                                                                ##STR472##       i-Bu                                                                               H   O  N                                              364                                                                                ##STR473##       i-Bu                                                                               H   O  N                                              365                                                                                ##STR474##       i-Bu                                                                               H   O  N                                              366                                                                                ##STR475##       i-Bu                                                                               H   O  N                                              367                                                                                ##STR476##       i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 52                                     __________________________________________________________________________     No.                                                                               R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     368                                                                                ##STR477##       i-Bu                                                                               H   O  CH                                             369                                                                                ##STR478##       i-Bu                                                                               H   O  CH                                             370                                                                                ##STR479##       i-Bu                                                                               H   O  CH 92-93                                                                                 ##STR480##                           371                                                                                ##STR481##       i-Bu                                                                               H   O  CH                                             372                                                                                ##STR482##       i-Bu                                                                               H   O  CH                                             373                                                                                ##STR483##       i-Bu                                                                               H   O  CH                                             374                                                                                ##STR484##       i-Bu                                                                               H   O  CH                                             375                                                                                ##STR485##       i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 53                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     376                                                                                ##STR486##       i-Bu                                                                               H   O  CH                                                                                       ##STR487##                           377                                                                                ##STR488##       i-Bu                                                                               H   O  CH                                             378                                                                                ##STR489##       i-Bu                                                                               H   O  CH                                             379                                                                                ##STR490##       i-Bu                                                                               H   O  CH                                             380                                                                                ##STR491##       i-Bu                                                                               H   O  CH                                             381                                                                                ##STR492##       i-Bu                                                                               H   O  CH                                                                                       ##STR493##                           382                                                                                ##STR494##       i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 54                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     383                                                                                ##STR495##       i-Bu                                                                               H   O  CH                                                                                       ##STR496##                           384                                                                                ##STR497##       i-Bu                                                                               H   O  CH                                             385                                                                                ##STR498##       i-Bu                                                                               H   O  CH                                             386                                                                                ##STR499##       i-Bu                                                                               H   O  CH 81.5-82.5                                                                             ##STR500##                           387                                                                                ##STR501##       i-Bu                                                                               H   O  CH                                             388                                                                                ##STR502##       i-Bu                                                                               H   O  CH                                             389                                                                                ##STR503##       i-Bu                                                                               H   O  CH                                             390                                                                                ##STR504##       i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 55                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     391                                                                                ##STR505##       i-Bu                                                                               H   O  CH                                             392                                                                                ##STR506##       i-Bu                                                                               H   O  CH                                             393                                                                                ##STR507##       i-Bu                                                                               H   O  CH                                             394                                                                                ##STR508##       i-Bu                                                                               H   O  CH                                             395                                                                                ##STR509##       i-Bu                                                                               H   O  CH                                             396                                                                                ##STR510##       i-Bu                                                                               H   O  CH                                             397                                                                                ##STR511##       i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 56                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     398                                                                                ##STR512##       i-Bu                                                                               H   O  CH                                             399                                                                                ##STR513##       i-Bu                                                                               H   O  CH                                             400                                                                                ##STR514##       i-Bu                                                                               H   O  CH                                             __________________________________________________________________________

                                      TABLE 57                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     401                                                                                ##STR515##       Me  4-MeO                                                                              O  CH 97.5-98.5                                                                             ##STR516##                           402                                                                                ##STR517##       Me  4-MeO                                                                              O  CH                                             403                                                                                ##STR518##       Me  4-MeO                                                                              O  CH 79.5-80.5                                                                             ##STR519##                           404                                                                                ##STR520##       Me  4-MeO                                                                              O  CH                                             405                                                                                ##STR521##       Me  4-MeO                                                                              O  CH                                             406                                                                                ##STR522##       Me  4-MeO                                                                              O  CH 71-72                                                                                 ##STR523##                           407                                                                                ##STR524##       Me  4-MeO                                                                              O  CH 121.5-122.5                                                                           ##STR525##                           __________________________________________________________________________

                                      TABLE 58                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     408                                                                                ##STR526##       Me  4-MeO                                                                              O  CH                                             409                                                                                ##STR527##       Me  4-MeO                                                                              O  CH 106-107                                                                               ##STR528##                           410                                                                                ##STR529##       Me  4-MeO                                                                              O  CH                                             411                                                                                ##STR530##       Me  4-MeO                                                                              O  CH                                             412                                                                                ##STR531##       Me  4-MeO                                                                              O  CH                                             413                                                                                ##STR532##       Me  4-MeO                                                                              O  CH                                             414                                                                                ##STR533##       Me  4-MeO                                                                              O  CH                                             415                                                                                ##STR534##       Me  4-MeO                                                                              O  CH                                                                                       ##STR535##                           __________________________________________________________________________

                                      TABLE 59                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     416                                                                                ##STR536##       Me        4-MeO                                                                              O  CH                                       417                                                                                ##STR537##       Me        4-MeO                                                                              O  CH                                       418                                                                                ##STR538##       Me        4-MeO                                                                              O  CH                                       419                                                                                ##STR539##       Me        4-MeO                                                                              O  CH                                       420                                                                                ##STR540##       Me        4-MeO                                                                              O  CH                                       421                                                                                ##STR541##       Me        4-MeO                                                                              O  CH                                       422                                                                                ##STR542##       Me        4-MeO                                                                              O  CH                                       423                                                                                ##STR543##       Me        4-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 60                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     424                                                                                ##STR544##       Me        4-MeO                                                                              O  CH                                       425                                                                                ##STR545##       Me        4-MeO                                                                              O  CH                                       426                                                                                ##STR546##       Me        4-MeO                                                                              O  CH                                                                                 ##STR547##                                                                         ##STR548##                       427                                                                                ##STR549##       Me        4-MeO                                                                              O  CH                                       428                                                                                ##STR550##       Me        4-MeO                                                                              O  CH                                       429                                                                                ##STR551##       Me        4-MeO                                                                              O  CH                                       430                                                                                ##STR552##       Me        4-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 61                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     431                                                                                ##STR553##       Me        4-MeO                                                                              O  CH                                       432                                                                                ##STR554##       Me        4-MeO                                                                              O  CH                                       433                                                                                ##STR555##       Me        4-MeO                                                                              O  CH                                                                                 ##STR556##                                                                         ##STR557##                       434                                                                                ##STR558##       Me        4-MeO                                                                              O  CH                                       435                                                                                ##STR559##       Me        4-MeO                                                                              O  CH                                       436                                                                                ##STR560##       Me        4-MeO                                                                              O  CH                                       437                                                                                ##STR561##       Me        4-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 62                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     438                                                                                ##STR562##       Me        4-MeO                                                                              O  CH                                       439                                                                                ##STR563##       Me        4-MeO                                                                              O  CH                                       440                                                                                ##STR564##       Me        4-MeO                                                                              O  CH                                       441                                                                                ##STR565##       Me        4-MeO                                                                              O  CH                                       442                                                                                ##STR566##       Me        4-MeO                                                                              O  CH                                       443                                                                                ##STR567##       Me        4-MeO                                                                              O  CH                                       444                                                                                ##STR568##       Me        4-MeO                                                                              O  CH                                       445                                                                                ##STR569##       Me        4-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 63                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     446                                                                                ##STR570##       Me        4-MeO                                                                              O  CH                                       447                                                                                ##STR571##       Me        4-MeO                                                                              O  CH                                       448                                                                                ##STR572##       Me        4-MeO                                                                              O  CH                                       449                                                                                ##STR573##       Me        4-MeO                                                                              O  CH                                       450                                                                                ##STR574##       Me        4-MeO                                                                              O  CH                                       451                                                                                ##STR575##       Me        4-MeO                                                                              O  CH                                       452                                                                               PhOCH.sub.2 CH.sub.2                                                                             Me        4-MeO                                                                              O  CH     3.85(3H, s), 3.92(2H, t,                                                       J=4.9), 4.00                                                                   (3H, s), 4.15(2H, t, J=4.9),                                                   6.51-7.33                                                                      (9H, m), 7.46(1H, d, J=8.5),                                                   7.84                                                                           (1H, s)                           __________________________________________________________________________

                                      TABLE 64                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     453                                                                               MeOCOCH.sub.2     Me        4-MeO                                                                              O  CH                                       454                                                                               PhCOCH.sub.2      Me        4-MeO                                                                              O  CH                                       455                                                                                ##STR576##       Me        4-MeO                                                                              S  CH                                       456                                                                                ##STR577##       Me        4-MeO                                                                              S  CH                                       457                                                                                ##STR578##       Me        4-MeO                                                                              S  CH                                       458                                                                                ##STR579##       Me        4-MeO                                                                              S  CH                                       459                                                                                ##STR580##       Me        4-MeO                                                                              S  CH                                       460                                                                                ##STR581##       Me        4-MeO                                                                              S  CH                                       __________________________________________________________________________

                                      TABLE 65                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     461                                                                                ##STR582##       Me  4-MeO                                                                              S  CH                                             462                                                                                ##STR583##       Me  4-MeO                                                                              O  N                                              463                                                                                ##STR584##       Me  4-MeO                                                                              O  N                                              464                                                                                ##STR585##       Me  4-MeO                                                                              O  N                                              465                                                                                ##STR586##       Me  4-MeO                                                                              O  N                                              466                                                                                ##STR587##       Me  4-MeO                                                                              O  N                                              467                                                                                ##STR588##       Me  4-MeO                                                                              O  CH                                             468                                                                                ##STR589##       Me  4-MeO                                                                              O  CH                                             __________________________________________________________________________

                                      TABLE 66                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     469                                                                                ##STR590##       Me  4-MeO                                                                              O  CH                                             470                                                                                ##STR591##       Me  4-MeO                                                                              O  CH 98.5-99.5                                                                             ##STR592##                           471                                                                                ##STR593##       Me  4-MeO                                                                              O  CH                                             472                                                                                ##STR594##       Me  4-MeO                                                                              O  CH                                             473                                                                                ##STR595##       Me  4-MeO                                                                              O  CH                                             474                                                                                ##STR596##       Me  4-MeO                                                                              O  CH                                             475                                                                                ##STR597##       Me  4-MeO                                                                              O  CH                                             __________________________________________________________________________

                                      TABLE 67                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     476                                                                                ##STR598##       Me  4-MeO                                                                              O  CH                                             477                                                                                ##STR599##       Me  4-MeO                                                                              O  CH                                             478                                                                                ##STR600##       Me  4-MeO                                                                              O  CH                                             479                                                                                ##STR601##       Me  4-MeO                                                                              O  CH                                             480                                                                                ##STR602##       Me  4-MeO                                                                              O  CH                                             481                                                                                ##STR603##       Me  4-MeO                                                                              O  CH                                                                                       ##STR604##                           482                                                                                ##STR605##       Me  4-MeO                                                                              O  CH                                             __________________________________________________________________________

                                      TABLE 68                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     483                                                                                ##STR606##       Me  4-MeO                                                                              O  CH                                                                                       ##STR607##                           484                                                                                ##STR608##       Me  4-MeO                                                                              O  CH                                             485                                                                                ##STR609##       Me  4-MeO                                                                              O  CH                                             486                                                                                ##STR610##       Me  4-MeO                                                                              O  CH                                             487                                                                                ##STR611##       Me  4-MeO                                                                              O  CH                                             488                                                                                ##STR612##       Me  4-MeO                                                                              O  CH                                             489                                                                                ##STR613##       Me  4-MeO                                                                              O  CH                                             490                                                                                ##STR614##       Me  4-MeO                                                                              O  CH                                             __________________________________________________________________________

                                      TABLE 69                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     491                                                                                ##STR615##       Me  H   O  CH                                                                                       ##STR616##                           492                                                                                ##STR617##       Me  H   O  CH                                                                                       ##STR618##                           493                                                                                ##STR619##       Me  H   O  CH                                             494                                                                                ##STR620##       Me  H   O  CH                                                                                       ##STR621##                           495                                                                                ##STR622##       Me  H   O  CH                                                                                       ##STR623##                           496                                                                                ##STR624##       Me  H   O  CH                                                                                       ##STR625##                           497                                                                                ##STR626##       Me  H   O  CH                                                                                       ##STR627##                           __________________________________________________________________________

                                      TABLE 70                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     498                                                                                ##STR628##       Me  4-MeO                                                                              O  CH                                             499                                                                                ##STR629##       Me  4-MeO                                                                              O  CH                                             500                                                                                ##STR630##       Me  4-MeO                                                                              O  CH                                             __________________________________________________________________________

                                      TABLE 71                                     __________________________________________________________________________     No R.sup.1           R.sup.2                                                                            R.sup.3                                                                            X  Y  mp(°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)              __________________________________________________________________________     501                                                                                ##STR631##       Me  5-Cl                                                                               O  CH 107-108.5                                                                             ##STR632##                           502                                                                                ##STR633##       Me  5-Cl                                                                               O  CH                                             503                                                                                ##STR634##       Me  5-Cl                                                                               O  CH 112-113                                                                               ##STR635##                           504                                                                                ##STR636##       Me  5-Cl                                                                               O  CH                                             505                                                                                ##STR637##       Me  5-Cl                                                                               O  CH                                             506                                                                                ##STR638##       Me  5-Cl                                                                               O  CH 107-108                                                                               ##STR639##                           507                                                                                ##STR640##       Me  5-Cl                                                                               O  CH 126-127                                                                               ##STR641##                           __________________________________________________________________________

                                      TABLE 72                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     508                                                                                ##STR642##       Me        5-Cl                                                                               O  CH                                       509                                                                                ##STR643##       Me        5-Cl                                                                               O  CH                                                                                 ##STR644##                                                                         ##STR645##                       510                                                                                ##STR646##       Me        5-Cl                                                                               O  CH                                       511                                                                                ##STR647##       Me        5-Cl                                                                               O  CH                                       512                                                                                ##STR648##       Me        5-Cl                                                                               O  CH                                       513                                                                                ##STR649##       Me        5-Cl                                                                               O  CH                                       514                                                                                ##STR650##       Me        5-Cl                                                                               O  CH                                       515                                                                                ##STR651##       Me        5-Cl                                                                               O  CH                                                                                 ##STR652##                                                                         ##STR653##                       __________________________________________________________________________

                                      TABLE 73                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     516                                                                                ##STR654##       Me        5-Cl                                                                               O  CH                                       517                                                                                ##STR655##       Me        5-Cl                                                                               O  CH                                       518                                                                                ##STR656##       Me        5-Cl                                                                               O  CH                                       519                                                                                ##STR657##       Me        5-Cl                                                                               O  CH                                       520                                                                                ##STR658##       Me        5-Cl                                                                               O  CH                                       521                                                                                ##STR659##       Me        5-Cl                                                                               O  CH                                       522                                                                                ##STR660##       Me        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 74                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     523                                                                                ##STR661##       Me        5-Cl                                                                               O  CH                                       524                                                                                ##STR662##       Me        5-Cl                                                                               O  CH                                       525                                                                                ##STR663##       Me        5-Cl                                                                               O  CH                                       526                                                                                ##STR664##       Me        5-Cl                                                                               O  CH                                                                                 ##STR665##                                                                         ##STR666##                       527                                                                                ##STR667##       Me        5-Cl                                                                               O  CH                                       528                                                                                ##STR668##       Me        5-Cl                                                                               O  CH                                       529                                                                                ##STR669##       Me        5-Cl                                                                               O  CH                                       530                                                                                ##STR670##       Me        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 75                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     531                                                                                ##STR671##       Me        5-Cl                                                                               O  CH                                                                                 ##STR672##                                                                         ##STR673##                       532                                                                                ##STR674##       Me        5-Cl                                                                               O  CH                                       533                                                                                ##STR675##       Me        5-Cl                                                                               O  CH                                                                                 ##STR676##                                                                         ##STR677##                       534                                                                                ##STR678##       Me        5-Cl                                                                               O  CH                                       535                                                                                ##STR679##       Me        5-Cl                                                                               O  CH                                       536                                                                                ##STR680##       Me        5-Cl                                                                               O  CH                                       537                                                                                ##STR681##       Me        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 76                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     538                                                                                ##STR682##       Me        5-Cl                                                                               O  CH                                       539                                                                                ##STR683##       Me        5-Cl                                                                               O  CH                                       540                                                                                ##STR684##       Me        5-Cl                                                                               O  CH                                       541                                                                                ##STR685##       Me        5-Cl                                                                               O  CH                                       542                                                                                ##STR686##       Me        5-Cl                                                                               O  CH                                       543                                                                                ##STR687##       Me        5-Cl                                                                               O  CH                                       544                                                                                ##STR688##       Me        5-Cl                                                                               O  CH                                       545                                                                                ##STR689##       Me        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 77                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     546                                                                                ##STR690##       Me        5-Cl                                                                               O  CH                                       547                                                                                ##STR691##       Me        5-Cl                                                                               O  CH                                       548                                                                                ##STR692##       Me        5-Cl                                                                               O  CH                                       549                                                                                ##STR693##       Me        5-Cl                                                                               O  CH                                       550                                                                                ##STR694##       Me        5-Cl                                                                               O  CH                                       551                                                                                ##STR695##       Me        5-Cl                                                                               O  CH                                       552                                                                               PhOCH.sub.2 CH.sub.2                                                                             Me        5-Cl                                                                               O  CH                                                                                 ##STR696##                                                                         ##STR697##                       __________________________________________________________________________

                                      TABLE 78                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     553                                                                               MeOCOCH.sub.2     Me        5-Cl                                                                               O  CH                                       554                                                                               PhCOCH.sub.2      Me        5-Cl                                                                               O  CH                                       555                                                                                ##STR698##       Me        5-Cl                                                                               S  CH                                       556                                                                                ##STR699##       Me        5-Cl                                                                               S  CH                                       557                                                                                ##STR700##       Me        5-Cl                                                                               S  CH                                       558                                                                                ##STR701##       Me        5-Cl                                                                               S  CH                                       559                                                                                ##STR702##       Me        5-Cl                                                                               S  CH                                       560                                                                                ##STR703##       Me        5-Cl                                                                               S  CH                                       __________________________________________________________________________

                                      TABLE 79                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     561                                                                                ##STR704##       Me        5-Cl                                                                               S  CH                                       562                                                                                ##STR705##       Me        5-Cl                                                                               O  N                                        563                                                                                ##STR706##       Me        5-Cl                                                                               O  N                                                                                      ##STR707##                       564                                                                                ##STR708##       Me        5-Cl                                                                               O  N                                        565                                                                                ##STR709##       Me        5-Cl                                                                               O  N                                                                                  ##STR710##                                                                         ##STR711##                       566                                                                                ##STR712##       Me        5-Cl                                                                               O  N                                        567                                                                                ##STR713##       Me        5-Cl                                                                               O  CH                                       568                                                                                ##STR714##       Me        5-Cl                                                                               O  CH                                                                                 ##STR715##                           __________________________________________________________________________

                                      TABLE 80                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     569                                                                                ##STR716##       Me        5-Cl                                                                               O  CH                                       570                                                                                ##STR717##       Me        5-Cl                                                                               O  CH                                                                                 ##STR718##                                                                         ##STR719##                       571                                                                                ##STR720##       Me        5-Cl                                                                               O  CH                                       572                                                                                ##STR721##       Me        5-Cl                                                                               O  CH                                       573                                                                                ##STR722##       Me        5-Cl                                                                               O  CH                                       574                                                                                ##STR723##       Me        5-Cl                                                                               O  CH                                       575                                                                                ##STR724##       Me        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 81                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     576                                                                                ##STR725##       Me        5-Cl                                                                               O  CH                                       577                                                                                ##STR726##       Me        5-Cl                                                                               O  CH                                       578                                                                                ##STR727##       Me        5-Cl                                                                               O  CH                                       579                                                                                ##STR728##       Me        5-Cl                                                                               O  CH                                       580                                                                                ##STR729##       Me        5-Cl                                                                               O  CH                                       581                                                                                ##STR730##       Me        5-Cl                                                                               O  CH                                                                                     ##STR731##                       582                                                                                ##STR732##       Me        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 82                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     583                                                                                ##STR733##       Me        5-Cl                                                                               O  CH                                                                                     ##STR734##                       584                                                                                ##STR735##       Me        5-Cl                                                                               O  CH                                       585                                                                                ##STR736##       Me        5-Cl                                                                               O  CH                                       586                                                                                ##STR737##       Me        5-Cl                                                                               O  CH                                       587                                                                                ##STR738##       Me        5-Cl                                                                               O  CH                                       588                                                                                ##STR739##       Me        5-Cl                                                                               O  CH                                       589                                                                                ##STR740##       Me        5-Cl                                                                               O  CH                                       590                                                                                ##STR741##       Me        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 83                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     591                                                                                ##STR742##       Me        5-Cl                                                                               O  CH                                       592                                                                                ##STR743##       Me        5-Cl                                                                               O  CH                                                                                     ##STR744##                       593                                                                                ##STR745##       Me        5-Cl                                                                               O  CH                                       594                                                                                ##STR746##       Me        5-Cl                                                                               O  CH                                       595                                                                                ##STR747##       Me        5-Cl                                                                               O  CH                                       596                                                                                ##STR748##       Me        5-Cl                                                                               O  CH                                       597                                                                                ##STR749##       Me        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 84                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     598                                                                                ##STR750##       Me        5-Cl                                                                               O  CH                                       599                                                                                ##STR751##       Me        5-Cl                                                                               O  CH                                       600                                                                                ##STR752##       Me        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 85                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     601                                                                                ##STR753##       n-Pr      H   O  CH                                       602                                                                                ##STR754##       n-Pr      H   O  CH                                       603                                                                                ##STR755##       n-Pr      H   O  CH                                                                                 ##STR756##                                                                         ##STR757##                       604                                                                                ##STR758##       n-Pr      H   O  CH                                       605                                                                                ##STR759##       n-Pr      H   O  CH                                       606                                                                                ##STR760##       n-Pr      H   O  CH                                                                                     ##STR761##                       607                                                                                ##STR762##       n-Pr      H   O  CH                                       __________________________________________________________________________

                                      TABLE 86                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     608                                                                                ##STR763##       n-Pr      H   O  CH                                       609                                                                                ##STR764##       n-Pr      H   O  CH                                                                                 ##STR765##                                                                         ##STR766##                       610                                                                                ##STR767##       n-Pr      H   O  CH                                       611                                                                                ##STR768##       n-Pr      H   O  CH                                       612                                                                                ##STR769##       n-Pr      H   O  CH                                       613                                                                                ##STR770##       n-Pr      H   O  CH                                       614                                                                                ##STR771##       n-Pr      H   O  CH                                       615                                                                                ##STR772##       n-Pr      H   O  CH                                                                                     ##STR773##                       __________________________________________________________________________

                                      TABLE 87                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     616                                                                                ##STR774##       i-Pr      H   O  CH                                       617                                                                                ##STR775##       i-Pr      H   O  CH                                       618                                                                                ##STR776##       i-Pr      H   O  CH                                                                                     ##STR777##                       619                                                                                ##STR778##       i-Pr      H   O  CH                                       620                                                                                ##STR779##       i-Pr      H   O  CH                                       621                                                                                ##STR780##       i-Pr      H   O  CH                                                                                 ##STR781##                                                                         ##STR782##                       622                                                                                ##STR783##       i-Pr      H   O  CH                                                                                 ##STR784##                                                                         ##STR785##                       __________________________________________________________________________

                                      TABLE 88                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     623                                                                                ##STR786##       i-Pr      H   O  CH                                       624                                                                                ##STR787##       i-Pr      H   O  CH                                                                                 ##STR788##                                                                         ##STR789##                       625                                                                                ##STR790##       i-Pr      H   O  CH                                       626                                                                                ##STR791##       i-Pr      H   O  CH                                       627                                                                                ##STR792##       i-Pr      H   O  CH                                       628                                                                                ##STR793##       i-Pr      H   O  CH                                       629                                                                                ##STR794##       i-Pr      H   O  CH                                       630                                                                                ##STR795##       i-Pr      H   O  CH                                                                                     ##STR796##                       __________________________________________________________________________

                                      TABLE 89                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     631                                                                                ##STR797##       n-Pr      H   O  N                                        632                                                                                ##STR798##       n-Pr      H   O  CH                                       633                                                                                ##STR799##       n-Pr      H   O  CH                                       634                                                                                ##STR800##       n-Pr      H   O  CH                                                                                     ##STR801##                       635                                                                                ##STR802##       n-Pr      H   O  CH                                                                                 ##STR803##                                                                         ##STR804##                       636                                                                                ##STR805##       n-Pr      H   O  CH                                       637                                                                                ##STR806##       n-Pr      H   O  CH                                       638                                                                                ##STR807##       n-Pr      H   O  CH                                       __________________________________________________________________________

                                      TABLE 90                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     639                                                                                ##STR808##       n-Pr      H   O  CH                                       640                                                                                ##STR809##       n-Pr      H   O  CH                                                                                     ##STR810##                       641                                                                                ##STR811##       n-Pr      H   O  CH                                       642                                                                                ##STR812##       n-Pr      H   O  CH                                       643                                                                                ##STR813##       n-Pr      H   O  CH                                       644                                                                                ##STR814##       n-Pr      H   O  CH                                       645                                                                                ##STR815##       n-Pr      H   O  CH                                       __________________________________________________________________________

                                      TABLE 91                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     646                                                                                ##STR816##       i-Pr      H   O  N                                        647                                                                                ##STR817##       i-Pr      H   O  CH                                       648                                                                                ##STR818##       i-Pr      H   O  CH                                       649                                                                                ##STR819##       i-Pr      H   O  CH                                                                                     ##STR820##                       650                                                                                ##STR821##       i-Pr      H   O  CH                                                                                 ##STR822##                                                                         ##STR823##                       651                                                                                ##STR824##       i-Pr      H   O  CH                                       652                                                                                ##STR825##       i-Pr      H   O  CH                                       __________________________________________________________________________

                                      TABLE 92                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     653                                                                                ##STR826##       i-Pr      H   O  CH                                       654                                                                                ##STR827##       i-Pr      H   O  CH                                       655                                                                                ##STR828##       i-Pr      H   O  CH                                                                                     ##STR829##                       656                                                                                ##STR830##       i-Pr      H   O  CH                                       657                                                                                ##STR831##       i-Pr      H   O  CH                                       658                                                                                ##STR832##       i-Pr      H   O  CH                                       659                                                                                ##STR833##       i-Pr      H   O  CH                                       660                                                                                ##STR834##       i-Pr      H   O  CH                                       __________________________________________________________________________

                                      TABLE 93                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     661                                                                                ##STR835##       Benzyl    H   O  CH                                                                                 ##STR836##                                                                         ##STR837##                       662                                                                                ##STR838##       Benzyl    H   O  CH                                       663                                                                                ##STR839##       Benzyl    H   O  CH                                       664                                                                                ##STR840##       Benzyl    H   O  CH                                       665                                                                                ##STR841##       FCH.sub.2 CH.sub.2                                                                       H   O  CH                                                                                 ##STR842##                                                                         ##STR843##                       666                                                                                ##STR844##       FCH.sub.2 CH.sub.2                                                                       H   O  CH                                       667                                                                                ##STR845##       FCH.sub.2 CH.sub.2                                                                       H   O  CH                                       __________________________________________________________________________

                                      TABLE 94                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     668                                                                                ##STR846##       FCH.sub.2 CH.sub.2                                                                       H   O  CH                                       669                                                                                ##STR847##                                                                                       ##STR848##                                                                              H   O  CH                                                                                 ##STR849##                                                                         ##STR850##                       670                                                                                ##STR851##                                                                                       ##STR852##                                                                              H   O  CH                                       671                                                                                ##STR853##                                                                                       ##STR854##                                                                              H   O  CH                                       672                                                                                ##STR855##                                                                                       ##STR856##                                                                              H   O  CH                                       673                                                                                ##STR857##       H         O   CH                                                                                    ##STR858##                           674                                                                                ##STR859##       H         O   CH                                          675                                                                                ##STR860##       H         O   CH                                          __________________________________________________________________________

                                      TABLE 95                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     676                                                                               H                 O         CH                                                                                  ##STR861##                                                                        ##STR862##                              677                                                                               H                 O         CH                                              678                                                                               H                 O         CH                                              679                                                                               H                 O         CH                                              680                                                                               H                 O         CH                                                                                  ##STR863##                                                                        ##STR864##                              681                                                                               H                 O         CH                                              682                                                                               H                 O         CH                                              __________________________________________________________________________

                                      TABLE 96                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     683                                                                                ##STR865##       H         O   CH                                          684                                                                               CICHCHCH.sub.2    H         O   CH                                                                                    ##STR866##                           685                                                                               CICHCHCH.sub.2    H         O   CH                                          686                                                                               CICHCHCH.sub.2    H         O   CH                                          687                                                                               CICHCHCH.sub.2    H         O   CH                                          688                                                                               Me                H         O   CH                                                                                    ##STR867##                           689                                                                               Et                H         O   CH                                          690                                                                               i-Bu              H         O   CH                                                                                    ##STR868##                      

    TABLE 97                                                                       __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     691                                                                               Me                5-Me      O   CH                                                                                 ##STR869##                              692                                                                               Me                5-Me      O   CH                                                                                 ##STR870##                              693                                                                               Me                5-Me      O   CH                                          694                                                                               Me                5-Me      O   CH                                                                                 ##STR871##                              695                                                                               Me                5-Me      O   CH                                          696                                                                               Me                5-Me      O   CH                                                                                 ##STR872##                              697                                                                               Me                5-Me      O   CH                                          __________________________________________________________________________

                                      TABLE 98                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     698                                                                               Me                5-Me      O   CH                                                                                    ##STR873##                           699                                                                               Me                5-Me      O   N                                           700                                                                               Me                5-Me      O   N                                           __________________________________________________________________________

                                      TABLE 99                                     __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     701                                                                               Me                5-F       O   CH                                                                                 ##STR874##                                                                        ##STR875##                           702                                                                               Me                5-F       O   CH                                          703                                                                               Me                5-F       O   CH                                                                                 ##STR876##                                                                        ##STR877##                           704                                                                               Me                5-F       O   CH                                          705                                                                               Me                5-F       O   CH                                          706                                                                               Me                5-F       O   CH                                                                                 ##STR878##                                                                        ##STR879##                           707                                                                               Me                5-F       O   CH                                                                                 ##STR880##                                                                        ##STR881##                           __________________________________________________________________________

                                      TABLE 100                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     708                                                                               Me                5-F       O   CH                                          709                                                                               Me                5-F       O   CH                                                                                 ##STR882##                                                                        ##STR883##                           710                                                                               Me                5-F       O   CH                                          711                                                                               Me                5-F       O   CH                                          712                                                                               Me                5-F       O   CH                                          713                                                                               Me                5-F       O   CH                                          714                                                                               Me                5-F       O   CH                                          715                                                                               Me                5-F       O   CH                                                                                 ##STR884##                                                                        ##STR885##                           __________________________________________________________________________

                                      TABLE 101                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     716                                                                               Me                5-F       O   CH                                          717                                                                               Me                5-F       O   CH                                          718                                                                               Me                5-F       O   CH                                          719                                                                               Me                5-F       O   CH                                          720                                                                               Me                5-F       O   CH                                          721                                                                               Me                5-F       O   CH                                          722                                                                               Me                5-F       O   CH                                          __________________________________________________________________________

                                      TABLE 102                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     723                                                                               Me                5-F       O   CH                                          724                                                                               Me                5-F       O   CH                                          725                                                                               Me                5-F       O   CH                                          726                                                                               Me                5-F       O   CH                                                                                 ##STR886##                                                                        ##STR887##                           727                                                                               Me                5-F       O   CH                                          728                                                                               Me                5-F       O   CH                                          729                                                                               Me                5-F       O   CH                                          730                                                                               Me                5-F       O   CH                                          __________________________________________________________________________

                                      TABLE 103                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     731                                                                                ##STR888##       Me        5-F O  CH                                                                                 ##STR889##                                                                         ##STR890##                       732                                                                                ##STR891##       Me        5-F O  CH                                       733                                                                                ##STR892##       Me        5-F O  CH                                                                                 ##STR893##                                                                         ##STR894##                       734                                                                                ##STR895##       Me        5-F O  CH                                       735                                                                                ##STR896##       Me        5-F O  CH                                       736                                                                                ##STR897##       Me        5-F O  CH                                       737                                                                                ##STR898##       Me        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 104                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     738                                                                                ##STR899##       Me        5-F O  CH                                       739                                                                                ##STR900##       Me        5-F O  CH                                       740                                                                                ##STR901##       Me        5-F O  CH                                       741                                                                                ##STR902##       Me        5-F O  CH                                       742                                                                                ##STR903##       Me        5-F O  CH                                       743                                                                                ##STR904##       Me        5-F O  CH                                       744                                                                                ##STR905##       Me        5-F O  CH                                       745                                                                                ##STR906##       Me        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 105                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     746                                                                                ##STR907##       Me        5-F O  CH                                       747                                                                                ##STR908##       Me        5-F O  CH                                       748                                                                                ##STR909##       Me        5-F O  CH                                       749                                                                                ##STR910##       Me        5-F O  CH                                       750                                                                                ##STR911##       Me        5-F O  CH                                       751                                                                                ##STR912##       Me        5-F O  CH                                       752                                                                               PhOCH.sub.2 CH.sub.2                                                                             Me        5-F O  CH                                                                                 ##STR913##                                                                         ##STR914##                       __________________________________________________________________________

                                      TABLE 106                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     753                                                                               MeOCOCH.sub.2     Me        5-F O  CH                                       754                                                                               PhCOCH.sub.2      Me        5-F O  CH                                       755                                                                                ##STR915##       Me        5-F S  CH                                       756                                                                                ##STR916##       Me        5-F S  CH                                       757                                                                                ##STR917##       Me        5-F S  CH                                       758                                                                                ##STR918##       Me        5-F S  CH                                       759                                                                                ##STR919##       Me        5-F S  CH                                       760                                                                                ##STR920##       Me        5-F S  CH                                       __________________________________________________________________________

                                      TABLE 107                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     761                                                                                ##STR921##       Me        5-F S  CH                                       762                                                                                ##STR922##       Me        5-F O  N                                        763                                                                                ##STR923##       Me        5-F O  N                                                                                      ##STR924##                       764                                                                                ##STR925##       Me        5-F O  N                                        765                                                                                ##STR926##       Me        5-F O  N                                                                                  ##STR927##                                                                         ##STR928##                       766                                                                                ##STR929##       Me        5-F O  N                                        767                                                                                ##STR930##       Me        5-F O  CH                                       768                                                                                ##STR931##       Me        5-F O  CH                                                                                 ##STR932##                           __________________________________________________________________________

                                      TABLE 108                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     769                                                                                ##STR933##       Me        5-F O  CH                                       770                                                                                ##STR934##       Me        5-F O  CH                                                                                 ##STR935##                                                                         ##STR936##                       771                                                                                ##STR937##       Me        5-F O  CH                                       772                                                                                ##STR938##       Me        5-F O  CH                                       773                                                                                ##STR939##       Me        5-F O  CH                                       774                                                                                ##STR940##       Me        5-F O  CH                                       775                                                                                ##STR941##       Me        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 109                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     776                                                                                ##STR942##       Me        5-F O  CH                                       777                                                                                ##STR943##       Me        5-F O  CH                                       778                                                                                ##STR944##       Me        5-F O  CH                                       779                                                                                ##STR945##       Me        5-F O  CH                                                                                     ##STR946##                       780                                                                                ##STR947##       Me        5-F O  CH                                       781                                                                                ##STR948##       Me        5-F O  CH                                                                                     ##STR949##                       782                                                                                ##STR950##       Me        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 110                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     783                                                                                ##STR951##       Me        5-F O  CH                                                                                     ##STR952##                       784                                                                                ##STR953##       Me        5-F O  CH                                       785                                                                                ##STR954##       Me        5-F O  CH                                       786                                                                                ##STR955##       Me        5-F O  CH                                       787                                                                                ##STR956##       Me        5-F O  CH                                       788                                                                                ##STR957##       Me        5-F O  CH                                       789                                                                                ##STR958##       Me        5-F O  CH                                       790                                                                                ##STR959##       Me        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 111                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     791                                                                                ##STR960##       Me        5-F O  CH                                       792                                                                                ##STR961##       Me        5-F O  CH                                                                                     ##STR962##                       793                                                                                ##STR963##       Me        5-F O  CH                                       794                                                                                ##STR964##       Me        5-F O  CH                                       795                                                                                ##STR965##       Me        5-F O  CH                                       796                                                                                ##STR966##       Me        5-F O  CH                                       797                                                                                ##STR967##       Me        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 112                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     798                                                                                ##STR968##       Me        5-F O  CH                                       799                                                                                ##STR969##       Me        5-F O  CH                                       800                                                                                ##STR970##       Me        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 113                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     801                                                                                ##STR971##       Me        3-Me                                                                               O  CH                                                                                     ##STR972##                       802                                                                                ##STR973##       Me        3-Me                                                                               O  CH                                       803                                                                                ##STR974##       Me        3-Me                                                                               O  CH                                                                                     ##STR975##                       804                                                                                ##STR976##       Me        3-Me                                                                               O  CH                                       805                                                                                ##STR977##       Me        3-Me                                                                               O  CH                                       806                                                                                ##STR978##       Me        3-Me                                                                               O  CH                                                                                     ##STR979##                       807                                                                                ##STR980##       Me        3-Me                                                                               O  CH                                                                                     ##STR981##                       __________________________________________________________________________

                                      TABLE 114                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     808                                                                                ##STR982##       Me        3-Me                                                                               O  CH                                       809                                                                                ##STR983##       Me        3-Me                                                                               O  CH                                                                                 ##STR984##                           810                                                                                ##STR985##       Me        3-Me                                                                               O  CH                                       811                                                                                ##STR986##       Me        3-Me                                                                               O  CH                                                                                     ##STR987##                       812                                                                                ##STR988##       Me        3-Me                                                                               O  CH                                       813                                                                                ##STR989##       Me        3-Me                                                                               O  CH                                       814                                                                                ##STR990##       Me        3-Me                                                                               O  CH                                       815                                                                                ##STR991##       Me        3-Me                                                                               O  CH                                                                                     ##STR992##                       __________________________________________________________________________

                                      TABLE 115                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     816                                                                                ##STR993##       Me        4-Me                                                                               O  CH                                                                                 ##STR994##                                                                         ##STR995##                       817                                                                                ##STR996##       Me        4-Me                                                                               O  CH                                       818                                                                                ##STR997##       Me        4-Me                                                                               O  CH                                                                                 ##STR998##                                                                         ##STR999##                       819                                                                                ##STR1000##      Me        4-Me                                                                               O  CH                                       820                                                                                ##STR1001##      Me        4-Me                                                                               O  CH                                       821                                                                                ##STR1002##      Me        4-Me                                                                               O  CH                                                                                 ##STR1003##                                                                        ##STR1004##                      822                                                                                ##STR1005##      Me        4-Me                                                                               O  CH                                                                                 ##STR1006##                                                                        ##STR1007##                      __________________________________________________________________________

                                      TABLE 116                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     823                                                                                ##STR1008##      Me        4-Me                                                                               O  CH                                       824                                                                                ##STR1009##      Me        4-Me                                                                               O  CH                                                                                 ##STR1010##                          825                                                                                ##STR1011##      Me        4-Me                                                                               O  CH                                       826                                                                                ##STR1012##      Me        4-Me                                                                               O  CH                                                                                 ##STR1013##                                                                        ##STR1014##                      827                                                                                ##STR1015##      Me        4-Me                                                                               O  CH                                       828                                                                                ##STR1016##      Me        4-Me                                                                               O  CH                                       829                                                                                ##STR1017##      Me        4-Me                                                                               O  CH                                       830                                                                                ##STR1018##      Me        4-Me                                                                               O  CH                                                                                     ##STR1019##                      __________________________________________________________________________

                                      TABLE 117                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     831                                                                                ##STR1020##      Me        3-Me                                                                               O  N                                                                                      ##STR1021##                      832                                                                                ##STR1022##      Me        3-Me                                                                               O  CH                                                                                     ##STR1023##                      833                                                                                ##STR1024##      Me        3-Me                                                                               O  CH                                       834                                                                                ##STR1025##      Me        3-Me                                                                               O  CH                                       835                                                                                ##STR1026##      Me        3-Me                                                                               O  CH                                                                                     ##STR1027##                      836                                                                                ##STR1028##      Me        3-Me                                                                               O  N                                                                                      ##STR1029##                      837                                                                                ##STR1030##      Me        3-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 118                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     838                                                                                ##STR1031##      Me        3-Me                                                                               O  CH                                                                                     ##STR1032##                      839                                                                                ##STR1033##      Me        3-Me                                                                               O  CH                                       840                                                                                ##STR1034##      Me        3-Me                                                                               O  CH                                                                                     ##STR1035##                      841                                                                                ##STR1036##      Me        3-Me                                                                               O  CH                                                                                     ##STR1037##                      842                                                                                ##STR1038##      Me        3-Me                                                                               O  CH                                                                                     ##STR1039##                      843                                                                                ##STR1040##      Me        3-Me                                                                               O  CH                                       844                                                                                ##STR1041##      Me        3-Me                                                                               O  CH                                       845                                                                                ##STR1042##      Me        3-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 119                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     846                                                                                ##STR1043##      Me        4-Me                                                                               O  N                                                                                  ##STR1044##                          847                                                                                ##STR1045##      Me        4-Me                                                                               O  CH                                                                                 ##STR1046##                          848                                                                                ##STR1047##      Me        4-Me                                                                               O  CH                                       849                                                                                ##STR1048##      Me        4-Me                                                                               O  CH                                       850                                                                                ##STR1049##      Me        4-Me                                                                               O  CH                                                                                 ##STR1050##                          851                                                                                ##STR1051##      Me        4-Me                                                                               O  N                                                                                  ##STR1052##                          852                                                                                ##STR1053##      Me        4-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 120                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     853                                                                                ##STR1054##      Me        4-Me                                                                               O  CH                                                                                     ##STR1055##                      854                                                                                ##STR1056##      Me        4-Me                                                                               O  CH                                       855                                                                                ##STR1057##      Me        4-Me                                                                               O  CH                                                                                     ##STR1058##                      856                                                                                ##STR1059##      Me        4-Me                                                                               O  CH                                                                                 ##STR1060##                          857                                                                                ##STR1061##      Me        4-Me                                                                               O  CH                                                                                     ##STR1062##                      858                                                                                ##STR1063##      Me        4-Me                                                                               O  CH                                       859                                                                                ##STR1064##      Me        4-Me                                                                               O  CH                                       860                                                                                ##STR1065##      Me        4-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 121                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     861                                                                                ##STR1066##      Me        H   O  CH                                       862                                                                                ##STR1067##      Me        H   O  CH                                       863                                                                                ##STR1068##      Me        H   O  CH                                                                                 ##STR1069##                          864                                                                                ##STR1070##      Me        H   O  CH                                       865                                                                                ##STR1071##      Me        H   O  CH                                       866                                                                                ##STR1072##      Me        H   O  CH                                                                                 ##STR1073##                          867                                                                                ##STR1074##      Et        H   O  CH                                       __________________________________________________________________________

                                      TABLE 122                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     868                                                                                ##STR1075##      Et        H   O  CH                                       869                                                                                ##STR1076##      Et        H   O  CH                                                                                 ##STR1077##                          870                                                                                ##STR1078##      Et        H   O  CH                                       871                                                                                ##STR1079##      Et        H   O  CH                                       872                                                                                ##STR1080##      Et        H   O  CH                                                                                     ##STR1081##                      873                                                                                ##STR1082##      Me        H   S  N                                        874                                                                                ##STR1083##      Me        H   S  N                                                                                      ##STR1084##                      875                                                                                ##STR1085##      Me        H   S  N                                        __________________________________________________________________________

                                      TABLE 123                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     876                                                                                ##STR1086##      Et        H   O  CH                                                                                     ##STR1087##                      877                                                                                ##STR1088##      Me        5-Cl                                                                               O  CH                                       878                                                                                ##STR1089##      Me        5-Cl                                                                               O  CH                                       879                                                                                ##STR1090##      Me        5-Cl                                                                               O  CH                                       880                                                                                ##STR1091##      Me        5-Cl                                                                               O  CH                                       881                                                                                ##STR1092##      Me        5-Cl                                                                               O  CH                                       882                                                                                ##STR1093##      Me        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 124                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     883                                                                                ##STR1094##      Me        5-F O  CH                                       884                                                                                ##STR1095##      Me        5-F O  CH                                       885                                                                                ##STR1096##      Me        5-F O  CH                                                                                 ##STR1097##                          886                                                                                ##STR1098##      Me        5-F O  CH                                       887                                                                                ##STR1099##      Me        5-F O  CH                                       888                                                                                ##STR1100##      Me        5-F O  CH                                                                                 ##STR1101##                          889                                                                                ##STR1102##      Me        5-F O  CH                                                                                 ##STR1103##                          890                                                                                ##STR1104##      Me        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 125                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     891                                                                                ##STR1105##      Me        5-Me                                                                               O  CH                                       892                                                                                ##STR1106##      Me        5-Me                                                                               O  CH                                       893                                                                                ##STR1107##      Me        5-Me                                                                               O  CH                                       894                                                                                ##STR1108##      Me        5-Me                                                                               O  CH                                       895                                                                                ##STR1109##      Me        5-Me                                                                               O  CH                                       896                                                                                ##STR1110##      Me        5-Me                                                                               O  CH                                       897                                                                                ##STR1111##      Me        5-Me                                                                               O  CH                                                                                     ##STR1112##                      __________________________________________________________________________

                                      TABLE 126                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     898                                                                                ##STR1113##      Me        5-Me                                                                               O  CH                                       899                                                                                ##STR1114##      Me        5-Me                                                                               O  CH                                       900                                                                                ##STR1115##      Me        6-Me                                                                               O  CH                                       901                                                                                ##STR1116##      Me        6-Me                                                                               O  CH                                       902                                                                                ##STR1117##      Me        6-Me                                                                               O  CH                                                                                     ##STR1118##                      903                                                                                ##STR1119##      Me        6-Me                                                                               O  CH                                       904                                                                                ##STR1120##      Me        6-Me                                                                               O  CH                                       905                                                                                ##STR1121##      Me        6-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 127                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     906                                                                                ##STR1122##      Me        H   O  CH                                                                                     ##STR1123##                      907                                                                                ##STR1124##      Me        5-Cl                                                                               O  CH                                       908                                                                                ##STR1125##      Me        5-F O  CH                                       909                                                                                ##STR1126##      Me        5-Me                                                                               O  CH                                       910                                                                                ##STR1127##      Et        H   O  CH                                                                                     ##STR1128##                      911                                                                                ##STR1129##      n-Pr      H   O  CH                                       912                                                                                ##STR1130##      i-Pr      H   O  CH                                       __________________________________________________________________________

                                      TABLE 128                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     913                                                                                ##STR1131##      Me        5-Me                                                                               O  CH                                                                                     ##STR1132##                      914                                                                                ##STR1133##      Me        5-Me                                                                               O  CH                                                                                     ##STR1134##                      915                                                                                ##STR1135##      Me        5-F O  CH                                       916                                                                                ##STR1136##      Me        5-Cl                                                                               O  CH                                                                                     ##STR1137##                      917                                                                                ##STR1138##      Me        5-Cl                                                                               O  CH                                                                                     ##STR1139##                      918                                                                                ##STR1140##      Me        5-Me                                                                               O  CH                                       919                                                                                ##STR1141##      Me        5-Me                                                                               O  CH                                       920                                                                                ##STR1142##      Me        5-Me                                                                               O  CH                                                                                     ##STR1143##                      __________________________________________________________________________

                                      TABLE 129                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     921                                                                                ##STR1144##      Me        5-MeO                                                                              O  CH                                                                                 ##STR1145##                          922                                                                                ##STR1146##      Me        5-MeO                                                                              O  CH                                       923                                                                                ##STR1147##      Me        5-MeO                                                                              O  CH                                       924                                                                                ##STR1148##      Me        5-MeO                                                                              O  CH                                       925                                                                                ##STR1149##      Me        5-MeO                                                                              O  CH                                       926                                                                                ##STR1150##      Me        5-MeO                                                                              O  CH                                                                                 ##STR1151##                          927                                                                                ##STR1152##      Me        5-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 130                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     928                                                                                ##STR1153##      Me        5-MeO                                                                              O  CH                                       929                                                                                ##STR1154##      Me        5-MeO                                                                              O  CH                                                                                 ##STR1155##                          930                                                                                ##STR1156##      Me        5-MeO                                                                              O  CH                                       931                                                                                ##STR1157##      Me        5-MeO                                                                              O  CH                                       932                                                                                ##STR1158##      Me        5-MeO                                                                              O  CH                                       933                                                                                ##STR1159##      Me        5-MeO                                                                              O  CH                                       934                                                                                ##STR1160##      Me        5-MeO                                                                              O  CH                                       935                                                                                ##STR1161##      Me        5-MeO                                                                              O  CH                                                                                 ##STR1162##                          __________________________________________________________________________

                                      TABLE 131                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     936                                                                                ##STR1163##      Me        5-MeO                                                                              O  CH                                       937                                                                                ##STR1164##      Me        5-MeO                                                                              O  CH                                                                                     ##STR1165##                      938                                                                                ##STR1166##      Me        5-MeO                                                                              O  CH                                                                                     ##STR1167##                      939                                                                                ##STR1168##      Me        5-MeO                                                                              O  CH                                       940                                                                                ##STR1169##      Me        5-MeO                                                                              O  CH                                                                                     ##STR1170##                      941                                                                                ##STR1171##      Me        5-MeO                                                                              O  CH                                       942                                                                                ##STR1172##      Me        5-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 132                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     943                                                                                ##STR1173##      Me        5-MeO                                                                              O  CH                                                                                 ##STR1174##                          944                                                                                ##STR1175##      Me        5-MeO                                                                              O  CH                                       945                                                                                ##STR1176##      Me        5-MeO                                                                              O  CH                                       946                                                                                ##STR1177##      Me        5-MeO                                                                              O  CH                                                                                 ##STR1178##                          947                                                                                ##STR1179##      Me        5-MeO                                                                              O  CH                                       948                                                                                ##STR1180##      Me        5-MeO                                                                              O  CH                                       949                                                                                ##STR1181##      Me        5-MeO                                                                              O  CH                                       950                                                                                ##STR1182##      Me        5-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 133                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     951                                                                                ##STR1183##      Et        5-MeO                                                                              O  CH                                                                                 ##STR1184##                          952                                                                                ##STR1185##      Et        5-MeO                                                                              O  CH                                       953                                                                                ##STR1186##      Et        5-MeO                                                                              O  CH                                       954                                                                                ##STR1187##      Et        5-MeO                                                                              O  CH                                       955                                                                                ##STR1188##      Et        5-MeO                                                                              O  CH                                       956                                                                                ##STR1189##      Et        5-MeO                                                                              O  CH                                                                                 ##STR1190##                          957                                                                                ##STR1191##      Et        5-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 134                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     958                                                                                ##STR1192##      Et        5-MeO                                                                              O  CH                                       959                                                                                ##STR1193##      Et        5-MeO                                                                              O  CH                                                                                 ##STR1194##                          960                                                                                ##STR1195##      Et        5-MeO                                                                              O  CH                                       961                                                                                ##STR1196##      Et        5-MeO                                                                              O  CH                                       962                                                                                ##STR1197##      Et        5-MeO                                                                              O  CH                                       963                                                                                ##STR1198##      Et        5-MeO                                                                              O  CH                                       964                                                                                ##STR1199##      Et        5-MeO                                                                              O  CH                                       965                                                                                ##STR1200##      Et        5-MeO                                                                              O  CH                                                                                 ##STR1201##                          __________________________________________________________________________

                                      TABLE 135                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     966                                                                                ##STR1202##      Et        5-MeO                                                                              O  CH                                       967                                                                                ##STR1203##      Et        5-MeO                                                                              O  CH                                                                                     ##STR1204##                      968                                                                                ##STR1205##      Et        5-MeO                                                                              O  CH                                                                                     ##STR1206##                      969                                                                                ##STR1207##      Et        5-MeO                                                                              O  CH                                       970                                                                                ##STR1208##      Et        5-MeO                                                                              O  CH                                                                                     ##STR1209##                      971                                                                                ##STR1210##      Et        5-MeO                                                                              O  CH                                       972                                                                                ##STR1211##      Et        5-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 136                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     973                                                                                ##STR1212##      Et        5-MeO                                                                              O  CH                                                                                 ##STR1213##                          974                                                                                ##STR1214##      Et        5-MeO                                                                              O  CH                                       975                                                                                ##STR1215##      Et        5-MeO                                                                              O  CH                                       976                                                                                ##STR1216##      Et        5-MeO                                                                              O  CH                                                                                     ##STR1217##                      977                                                                                ##STR1218##      Et        5-MeO                                                                              O  CH                                       978                                                                                ##STR1219##      Et        5-MeO                                                                              O  CH                                       979                                                                                ##STR1220##      Et        5-MeO                                                                              O  CH                                       980                                                                                ##STR1221##      Et        5-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 137                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     981                                                                                ##STR1222##      Et        5-Me                                                                               O  CH                                       982                                                                                ##STR1223##      Et        5-Me                                                                               O  CH                                       983                                                                                ##STR1224##      Et        5-Me                                                                               O  CH                                       984                                                                                ##STR1225##      Et        5-Me                                                                               O  CH                                       985                                                                                ##STR1226##      Et        5-Me                                                                               O  CH                                       986                                                                                ##STR1227##      Et        5-Me                                                                               O  CH                                                                                 ##STR1228##                          987                                                                                ##STR1229##      Et        5-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 138                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     988                                                                                ##STR1230##      Et        5-Me                                                                               O  CH                                       989                                                                                ##STR1231##      Et        5-Me                                                                               O  CH                                                                                 ##STR1232##                          990                                                                                ##STR1233##      Et        5-Me                                                                               O  CH                                       991                                                                                ##STR1234##      Et        5-Me                                                                               O  CH                                       992                                                                                ##STR1235##      Et        5-Me                                                                               O  CH                                       993                                                                                ##STR1236##      Et        5-Me                                                                               O  CH                                       994                                                                                ##STR1237##      Et        5-Me                                                                               O  CH                                       995                                                                                ##STR1238##      Et        5-Me                                                                               O  CH                                                                                 ##STR1239##                          __________________________________________________________________________

                                      TABLE 139                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     996                                                                                ##STR1240##      Et        5-Me                                                                               O  CH                                       997                                                                                ##STR1241##      Et        5-Me                                                                               O  CH                                                                                     ##STR1242##                      998                                                                                ##STR1243##      Et        5-Me                                                                               O  CH                                                                                     ##STR1244##                      999                                                                                ##STR1245##      Et        5-Me                                                                               O  CH                                       1000                                                                               ##STR1246##      Et        5-Me                                                                               O  CH                                                                                 ##STR1247##                          1001                                                                               ##STR1248##      Et        5-Me                                                                               O  CH                                       1002                                                                               ##STR1249##      Et        5-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 140                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1003                                                                               ##STR1250##      Et        5-Me                                                                               O  CH                                                                                     ##STR1251##                      1004                                                                               ##STR1252##      Et        5-Me                                                                               O  CH                                       1005                                                                               ##STR1253##      Et        5-Me                                                                               O  CH                                       1006                                                                               ##STR1254##      Et        5-Me                                                                               O  CH                                                                                 ##STR1255##                          1007                                                                               ##STR1256##      Et        5-Me                                                                               O  CH                                       1008                                                                               ##STR1257##      Et        5-Me                                                                               O  CH                                       1009                                                                               ##STR1258##      Et        5-Me                                                                               O  CH                                       1010                                                                               ##STR1259##      Et        5-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 141                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1011                                                                               ##STR1260##      Et        5-F O  CH                                       1012                                                                               ##STR1261##      Et        5-F O  CH                                       1013                                                                               ##STR1262##      Et        5-F O  CH                                       1014                                                                               ##STR1263##      Et        5-F O  CH                                       1015                                                                               ##STR1264##      Et        5-F O  CH                                       1016                                                                               ##STR1265##      Et        5-F O  CH                                                                                     ##STR1266##                      1017                                                                               ##STR1267##      Et        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 142                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1018                                                                               ##STR1268##      Et        5-F O  CH                                       1019                                                                               ##STR1269##      Et        5-F O  CH                                                                                     ##STR1270##                      1020                                                                               ##STR1271##      Et        5-F O  CH                                       1021                                                                               ##STR1272##      Et        5-F O  CH                                       1022                                                                               ##STR1273##      Et        5-F O  CH                                       1023                                                                               ##STR1274##      Et        5-F O  CH                                       1024                                                                               ##STR1275##      Et        5-F O  CH                                       1025                                                                               ##STR1276##      Et        5-F O  CH                                                                                     ##STR1277##                      __________________________________________________________________________

                                      TABLE 143                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1026                                                                               ##STR1278##      Et        5-F O  CH                                       1027                                                                               ##STR1279##      Et        5-F O  CH                                                                                     ##STR1280##                      1028                                                                               ##STR1281##      Et        5-F O  CH                                                                                     ##STR1282##                      1029                                                                               ##STR1283##      Et        5-F O  CH                                       1030                                                                               ##STR1284##      Et        5-F O  CH                                                                                     ##STR1285##                      1031                                                                               ##STR1286##      Et        5-F O  CH                                       1032                                                                               ##STR1287##      Et        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 144                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1033                                                                               ##STR1288##      Et        5-F O  CH                                                                                     ##STR1289##                      1034                                                                               ##STR1290##      Et        5-F O  CH                                       1035                                                                               ##STR1291##      Et        5-F O  CH                                       1036                                                                               ##STR1292##      Et        5-F O  CH                                                                                     ##STR1293##                      1037                                                                               ##STR1294##      Et        5-F O  CH                                       1038                                                                               ##STR1295##      Et        5-F O  CH                                       1039                                                                               ##STR1296##      Et        5-F O  CH                                       1040                                                                               ##STR1297##      Et        5-F O  CH                                       __________________________________________________________________________

                                      TABLE 145                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1041                                                                               ##STR1298##      Et        5-Cl                                                                               O  CH                                                                                 ##STR1299##                          1042                                                                               ##STR1300##      Et        5-Cl                                                                               O  CH                                       1043                                                                               ##STR1301##      Et        5-Cl                                                                               O  CH                                       1044                                                                               ##STR1302##      Et        5-Cl                                                                               O  CH                                       1045                                                                               ##STR1303##      Et        5-Cl                                                                               O  CH                                       1046                                                                               ##STR1304##      Et        5-Cl                                                                               O  CH                                                                                 ##STR1305##                          1047                                                                               ##STR1306##      Et        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 146                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1048                                                                               ##STR1307##      Et        5-Cl                                                                               O  CH                                       1049                                                                               ##STR1308##      Et        5-Cl                                                                               O  CH                                                                                 ##STR1309##                          1050                                                                               ##STR1310##      Et        5-Cl                                                                               O  CH                                       1051                                                                               ##STR1311##      Et        5-Cl                                                                               O  CH                                       1052                                                                               ##STR1312##      Et        5-Cl                                                                               O  CH                                       1053                                                                               ##STR1313##      Et        5-Cl                                                                               O  CH                                       1054                                                                               ##STR1314##      Et        5-Cl                                                                               O  CH                                       1055                                                                               ##STR1315##      Et        5-Cl                                                                               O  CH                                                                                 ##STR1316##                          __________________________________________________________________________

                                      TABLE 147                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1056                                                                               ##STR1317##      Et        5-Cl                                                                               O  CH                                       1057                                                                               ##STR1318##      Et        5-Cl                                                                               O  CH                                                                                     ##STR1319##                      1058                                                                               ##STR1320##      Et        5-Cl                                                                               O  CH                                                                                     ##STR1321##                      1059                                                                               ##STR1322##      Et        5-Cl                                                                               O  CH                                       1060                                                                               ##STR1323##      Et        5-Cl                                                                               O  CH                                                                                 ##STR1324##                          1061                                                                               ##STR1325##      Et        5-Cl                                                                               O  CH                                       1062                                                                               ##STR1326##      Et        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 148                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1063                                                                               ##STR1327##      Et        5-Cl                                                                               O  CH                                                                                     ##STR1328##                      1064                                                                               ##STR1329##      Et        5-Cl                                                                               O  CH                                       1065                                                                               ##STR1330##      Et        5-Cl                                                                               O  CH                                       1066                                                                               ##STR1331##      Et        5-Cl                                                                               O  CH                                                                                     ##STR1332##                      1067                                                                               ##STR1333##      Et        5-Cl                                                                               O  CH                                       1068                                                                               ##STR1334##      Et        5-Cl                                                                               O  CH                                       1069                                                                               ##STR1335##      Et        5-Cl                                                                               O  CH                                       1070                                                                               ##STR1336##      Et        5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 149                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1071                                                                               ##STR1337##      Allyl     5-Cl                                                                               O  CH                                       1072                                                                               ##STR1338##      Allyl     5-Cl                                                                               O  CH                                       1073                                                                               ##STR1339##      Allyl     5-Cl                                                                               O  CH                                       1074                                                                               ##STR1340##      Allyl     5-Cl                                                                               O  CH                                       1075                                                                               ##STR1341##      Allyl     5-Cl                                                                               O  CH                                       1076                                                                               ##STR1342##      Allyl     5-Cl                                                                               O  CH                                       1077                                                                               ##STR1343##      Allyl     5-F O  CH                                       __________________________________________________________________________

                                      TABLE 150                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1078                                                                               ##STR1344##      Allyl     5-F O  CH                                       1079                                                                               ##STR1345##      Allyl     5-F O  CH                                       1080                                                                               ##STR1346##      Allyl     5-F O  CH                                       1081                                                                               ##STR1347##      Allyl     5-F O  CH                                       1082                                                                               ##STR1348##      Allyl     5-F O  CH                                       1083                                                                               ##STR1349##      Allyl     5-Me                                                                               O  CH                                       1084                                                                               ##STR1350##      Allyl     5-Me                                                                               O  CH                                       1085                                                                               ##STR1351##      Allyl     5-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 151                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1086                                                                               ##STR1352##      Allyl     5-Me                                                                               O  CH                                       1087                                                                               ##STR1353##      Allyl     5-Me                                                                               O  CH                                       1088                                                                               ##STR1354##      Allyl     5-Me                                                                               O  CH                                       1089                                                                               ##STR1355##      Allyl     5-MeO                                                                              O  CH                                       1090                                                                               ##STR1356##      Allyl     5-MeO                                                                              O  CH                                       1091                                                                               ##STR1357##      Allyl     5-MeO                                                                              O  CH                                       1092                                                                               ##STR1358##      Allyl     5-MeO                                                                              O  CH                                       __________________________________________________________________________

                                      TABLE 152                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1093                                                                               ##STR1359##      Allyl     5-MeO                                                                              O  CH                                       1094                                                                               ##STR1360##      Allyl     5-MeO                                                                              O  CH                                       1095                                                                               ##STR1361##      i-Bu      5-Cl                                                                               O  CH                                       1096                                                                               ##STR1362##      i-Bu      5-Cl                                                                               O  CH                                       1097                                                                               ##STR1363##      i-Bu      5-Cl                                                                               O  CH                                       1098                                                                               ##STR1364##      i-Bu      5-Cl                                                                               O  CH                                       1099                                                                               ##STR1365##      i-Bu      5-Cl                                                                               O  CH                                       1100                                                                               ##STR1366##      i-Bu      5-Cl                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 153                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1101                                                                               ##STR1367##      Me        5-F O  CH                                                                                     ##STR1368##                      1102                                                                               ##STR1369##      Me        5-Cl                                                                               O  CH                                       1103                                                                               ##STR1370##      Me        5-Cl                                                                               O  CH                                       1104                                                                               ##STR1371##      Me        5-MeO                                                                              O  CH                                                                                     ##STR1372##                      1105                                                                               ##STR1373##      Me        5-Me                                                                               O  CH                                       1106                                                                               ##STR1374##      Me        5-Me                                                                               O  CH                                       1107                                                                               ##STR1375##      Me        5-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 154                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1108                                                                               ##STR1376##      Me        5-Me                                                                               O  CH                                       1109                                                                               ##STR1377##      Me        5-Me                                                                               O  CH                                       1110                                                                               ##STR1378##      Me        H   O  CH                                       1111                                                                               ##STR1379##      Me        5-F O  CH                                       1112                                                                               ##STR1380##      Me        5-Cl                                                                               O  CH                                       1113                                                                               ##STR1381##      Me        5-Me                                                                               O  CH                                       1114                                                                               ##STR1382##      Me        5-MeO                                                                              O  CH                                       1115                                                                               ##STR1383##      Et        H   O  CH                                       __________________________________________________________________________

                                      TABLE 155                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1116                                                                               ##STR1384##      Me        5-F O  CH                                       1117                                                                               ##STR1385##      Me        5-Cl                                                                               O  CH                                       1118                                                                               ##STR1386##      Me        5-F O  CH                                       1119                                                                               ##STR1387##      Me        5-Me                                                                               O  CH                                       1120                                                                               ##STR1388##      Me        5-Cl                                                                               O  CH                                       1121                                                                               ##STR1389##      Allyl     H   O  CH                                       1122                                                                               ##STR1390##      Me        5-Me                                                                               O  CH                                       1123                                                                               ##STR1391##      Me        5-Me                                                                               O  CH                                       1124                                                                               ##STR1392##      Me        5-Me                                                                               O  CH                                       __________________________________________________________________________

                                      TABLE 156                                    __________________________________________________________________________                                              mp                                    No R.sup.1           R.sup.2   R.sup.3                                                                            X  Y  (°C.)                                                                       .sup.1 H-NMR(CDCl.sub.3)          __________________________________________________________________________     1125                                                                               ##STR1393##      Me        5-Me                                                                               O  CH                                       1126                                                                               ##STR1394##      Et        H   O  CH                                                                                     ##STR1395##                      1127                                                                               ##STR1396##      Et        5-F O  CH                                       1128                                                                               ##STR1397##      Et        5-Cl                                                                               O  CH                                                                                     ##STR1398##                      1129                                                                               ##STR1399##      Et        5-Me                                                                               O  CH                                                                                     ##STR1400##                      1130                                                                               ##STR1401##      Et        5-MeO                                                                              O  CH                                                                                     ##STR1402##                      __________________________________________________________________________

The following examples illustrate the production of the fungicidal compositions of the present invention.

Example 14

A mixture of 2 parts of the Compound No. 9 and 98 parts of talc was pulverized to obtain a powder.

Example 15

A suspension was prepared by mixing 40 parts of Compound No. 9, 10 parts of sodium lignin sulfonate and 50 parts of water.

Example 16

A solution was prepared by mixing 10 parts of Compound No. 9, 1 part of Tween 20 (trade mark) and 89 parts of isopropyl alcohol.

Example 17

A wettable powder was prepared by mixing 50 parts of Compound No. 83, 6 parts of sodium alkylbenzenesulfonate, 4 parts of sodium lignin sulfonate and 40 parts of clay and pulverizing the mixture.

Example 18

Granules were prepared by mixing 5 parts of Compound No. 83, 90 parts of a mixture of equal amounts of bentonite and talc and 5 parts of sodium alkylbenzene sulfonate, pulverizing the mixture and granulating the pulverized mixture.

Example 19

An emulsion was prepared by mixing and dispersing 25 parts of Compound No. 83, 8 parts of polyoxyethylene alkylphenyl ether, 2 parts of sodium alkylbenzene sulfonate and 65 parts of xylene.

The following examples illustrate the production of the herbicidal and growth regulating compositions.

Example 20

    ______________________________________                                                          Parts by weight                                               ______________________________________                                         Compound No. 9     50                                                          Clay               45                                                          Emal (trade mark, spreader                                                                         5                                                          manufactured by Kao Corp.)                                                     ______________________________________                                    

The above ingredients were mixed to give a wettable powder.

Example 21

    ______________________________________                                                                Parts by weight                                         ______________________________________                                         Compound No. 9           20                                                    Xylene                   65                                                    Sorpol 3005X (trade mark, spreader                                                                      15                                                    manufacutured by Tohoh Kagaku Kogyo K.K.)                                      ______________________________________                                    

Compound No. 9 was dissolved in xylene and Sorpol was added to give an emulsifiable concentrate.

Example 22

    ______________________________________                                                                Parts by weight                                         ______________________________________                                         Compound No. 83           3                                                    Sorpol 5060 (trade mark, spreader                                                                        3                                                    manufactured by Tohoh Kagaku Kogyo K.K.)                                       Bentonite                40                                                    Talc                     20                                                    Clay                     34                                                    ______________________________________                                    

The above ingredients were mixed homogeneously and binded by adding water and subjected to extrusion to give granules.

Example 23

    ______________________________________                                                                Parts by weight                                         ______________________________________                                         Compound No. 83          3                                                     Emulgen 910 (trade mark, nonionic surfactant                                                            1                                                     manufactured by Kao Corp.)                                                     Solvent naphtha          5                                                     Granular bentonite       91                                                    ______________________________________                                    

Compound No. 83 and Emulgen were dissolved in solvent naphtha. The granular bentonite was spray-coated with this solution to obtain granules.

Test Examples

The following pot experiments show controlling effect of the various compounds of the present invention on plant diseases by foliar treatment.

Experimental Method

In experiments for determination of preventive effect, a liquid sample to be tested was sprayed to test plants and pathogens were inoculated after 24 hours. In experiments for determination of curative effect, the test plants were inoculated with each pathogen, and when slight lesions were observed (24 to 48 hours after the inoculation), a liquid sample to be tested was sprayed to the test plants.

The liquid sample was prepared by dissolving the test compound in a small amount of N,N-dimethylformamide and diluting the solution with distilled water containing a spreader to a given concentration.

The percent control was calculated according to the following equation: ##EQU1##

Test Example 1 Controlling effect on Pyricularia oryzae

Two-week rice seedlings (var.: AICHIASAHI) were transplanted in plastic cups (each 9 cmφ) and cultivated another 2 weeks. The test compound in the form of a solution or a suspension was sprayed to the foliage of the rice seedlings, to which a conidia suspension of Pyricularia oryzae cultured in an oatmeal medium was inoculated by spraying. The test plant was kept in a moist chamber (28° C., 100% R.H.) for 24 hours, followed by cultivation in a greenhouse for 5 days. As the control, fthalide (4,5,6,7-tetrachlorophthalide) was used. Six days after inoculation, the number of lesions of the plant was measured and the preventive effect was calculated. The results are shown in Tablea 157 to 159.

In the following Tables 157 to 164, P.o. means Pyricularia oryzae, S.f. means Sphaerotheca fuliginea., B.c. means Botrytis cinerea, E.g. means Erysiphe graminis f. sp. frifici, pre means preventive treatment, and sup means curative treatment.

                  TABLE 157                                                        ______________________________________                                                            P.o. (%)                                                    Compound No. (125 ppm)                                                                              pre    sup                                                ______________________________________                                          3                   90     97                                                  7                   90     97                                                  9                   70     97                                                  55                  90     97                                                  58                  95     97                                                  68                  90     97                                                  70                  90     97                                                  83                  97     97                                                 103                  90     97                                                 106                  90     97                                                 109                  90     97                                                 115                  90     97                                                 131                  70     90                                                 152                         100                                                155                  97     97                                                 168                  90     97                                                 170                  90     97                                                 183                  97     97                                                 184                  93     90                                                 189                  90     90                                                 196                  97     70                                                 203                  90     90                                                 233                  90     90                                                 270                  90     90                                                 ______________________________________                                    

                  TABLE 158                                                        ______________________________________                                                            P.o. (%)                                                    Compound No. (125 ppm)                                                                              pre    sup                                                ______________________________________                                         283                  90     90                                                 306                  90     90                                                 315                  90     90                                                 492                  90     97                                                 494                  90     97                                                 495                  95     97                                                 552                  95     97                                                 581                  95     95                                                 583                  95     95                                                 609                  90     90                                                 624                  95     90                                                 640                  93     95                                                 655                  90     90                                                 665                  90     95                                                 669                  95     95                                                 698                  90     90                                                 703                  95     90                                                 731                  95     90                                                 803                  90     90                                                 866                  90     90                                                 869                  90     90                                                 872                  90     90                                                 876                  97     97                                                 885                  90     97                                                 ______________________________________                                    

                  TABLE 159                                                        ______________________________________                                                            P.o. (%)                                                    Compound No. (125 ppm)                                                                              pre    sup                                                ______________________________________                                         888                  90     90                                                 889                  97     90                                                 937                  90     90                                                 940                  97     97                                                 946                  90     90                                                 959                  95     97                                                 970                  90     90                                                 986                  90     90                                                 1016                 93     97                                                 1030                 93     97                                                 1046                 95     90                                                 1066                 95     97                                                 Control              90     97                                                 ______________________________________                                    

Test Example 2

Controlling effect on cucumber powdery mildew (Sphaerotheca fuliginea)

Seeds of cucumber (var.: TSUKUBASHIROIBO) were sown in plastic cups (each 9 cm in diameter), followed by cultivation for 2 to 3 weeks. A liquid test sample in the form of a solution or suspension was sprayed on the surface of their first leaves. The pathogen was inoculated by spraying to the leaves a conidia suspension of Sphaerotheca fuliginea which had been cultured on the cucumber leaves. The plants were kept in a greenhouse at 20° C. for 10 days. The infected area on the leaf was observed, and the percent control was calculated. As the control, fenarimol {2,4'-dichloro-2-(pyrimidin-5-yl)benzhydryl alcohol} was used. The results are shown in Table 160.

                  TABLE 160                                                        ______________________________________                                                            S.f. (%)                                                    Compound No. (125 ppm)                                                                              pre    sup                                                ______________________________________                                          1                   100    100                                                 3                   100    100                                                 7                   100    100                                                 9                   100    100                                                 15                  100    100                                                 51                  100    100                                                 52                  100    100                                                 55                   85     95                                                 65                   85     90                                                 68                  100    100                                                 70                  100    100                                                 83                  100    100                                                107                  100    100                                                109                  100    100                                                131                  100    100                                                152                  100                                                       155                  100    100                                                165                   95    100                                                168                  100    100                                                170                  100    100                                                183                  100    100                                                Control              100    100                                                ______________________________________                                    

Test Example 3

Controlling effect on Botrytis cinerea

The seeds of cucumber (var.: TSUKUBASHIROIBO) were sown in plastic cups (9 cmφ), followed by cultivation for 2 to 3 weeks. The test compound in the form of a solution or suspension was sprayed to the surface of their first leaves, and the cucumber seedlings were inoculated with mycelial disks (4 mmφ) of Botrytis cinerea cultured on the potato sucrose agar medium by putting the disks on the leaf surfaces. The plants were kept in a moist chamber at 20° C. for 2 days. The diameter of the lesions on the leaves was measured and the percent control was calculated. As the control, iprodione {3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide} was used. The results are shown in Table 161.

                  TABLE 161                                                        ______________________________________                                                            B.c.                                                        Compound No. (125 ppm)                                                                              pre    sup                                                ______________________________________                                          1                   100    70                                                  3                   100    70                                                  7                   100    50                                                  15                  100    70                                                  68                  90     50                                                 106                  100    50                                                 109                  70     30                                                 152                  70     50                                                 501                  100    30                                                 503                  100    30                                                 526                  70     30                                                 691                  100    30                                                 694                  70     30                                                 701                  90     70                                                 707                  100    30                                                 715                  90     50                                                 726                  100    30                                                 926                  90     50                                                 935                  100    30                                                 940                  90     70                                                 965                  70     30                                                 995                  70     30                                                 Control              90     87                                                 ______________________________________                                    

Test Example 4

Controlling effect on Erysiphe graminis f. sp. frifici

The seeds of wheat (var.: NORIN No. 61) were sown in plastic cups (9 cmφ), followed by cultivation for 2 to 3 weeks. The test compound in the form of a solution or suspension was sprayed to the seedlings, and the seedlings were inoculated with conidia of Erysiphe graminis f. sp. frifici cultured on the wheat leaves by putting the conidia on the test plants. The plants were kept in a greenhouse at 20° C. for 10 days. The infected area on the leaf was observed, and the percent control was calculated. As the control, fenarimol was used. The results are shown in Tables 162 to 164.

                  TABLE 162                                                        ______________________________________                                                            E.g.                                                        Compound No. (125 ppm)                                                                              pre    sup                                                ______________________________________                                          62                  90     90                                                  63                  90     90                                                 209                  97     97                                                 253                  97     97                                                 483                  97     97                                                 491                  97     97                                                 492                  100    97                                                 494                  90     97                                                 496                  90     97                                                 497                  97     97                                                 531                  90     97                                                 563                  97     90                                                 568                  97     90                                                 581                  97     90                                                 592                  90     70                                                 603                  90     90                                                 606                  97     90                                                 621                  97     97                                                 622                  97     90                                                 635                  90     90                                                 649                  97     90                                                 650                  97     90                                                 ______________________________________                                    

                  TABLE 163                                                        ______________________________________                                                            E.g.                                                        Compound No. (125 ppm)                                                                              pre    sup                                                ______________________________________                                         692                  90     90                                                 706                  97     97                                                 707                  90     90                                                 752                  90     97                                                 765                  90     90                                                 768                  97     97                                                 770                  97     97                                                 779                  97     97                                                 781                  97     90                                                 783                  90     90                                                 831                  97     90                                                 838                  97     70                                                 855                  97     90                                                 889                  90     97                                                 902                  90     97                                                 913                  90     90                                                 914                  90     97                                                 916                  97     97                                                 929                  97     90                                                 938                  97     97                                                 943                  90     97                                                 956                  70     97                                                 ______________________________________                                    

                  TABLE 164                                                        ______________________________________                                                            E.g.                                                        Compound No. (125 ppm)                                                                              pre    sup                                                ______________________________________                                          967                 90     97                                                  968                 90     97                                                  973                 90     97                                                  976                 70     97                                                  997                 97     97                                                  998                 97     70                                                 1000                 97     70                                                 1003                 97     97                                                 1025                 97     97                                                 1027                 97     97                                                 1028                 97     97                                                 1033                 97     97                                                 1036                 97     90                                                 1057                 97     97                                                 1058                 90     97                                                 1063                 90     97                                                 1101                 97     97                                                 1104                 90     90                                                 1126                 90     97                                                 1128                 70     97                                                 1129                 97     97                                                 Control              97     97                                                 ______________________________________                                    

The following experiment shows herbicidal and growth regulating activities of the compounds of the present invention.

Test Example 5 (herbicidal activity)

As the test plants, Echinochloa oryzicola, Monochoria vaginalis and Scirpus juncoides were used.

A square-shaped pot (7.1×7.1 cm) was charged with paddy soil. The seeds (10 seeds/pot) of the above plants were sown in the soil and submerged in water (2 cm). Immediately after that, the test compound (40 g ai/a) was diluted with water (0.7 ml/pot) and treated on the water surface of each pot.

Three weeks after the treatment, the effects of the compound (inhibition of germination and growth, deformation, leaf dying, withering, etc.) were observed. The criteria for the evaluation were grouped into the following six grades: 0 (harmless) to 5 (withering).

The second screening was carried out when the maximum activity (5) was observed in the gramineous plant, broad-leaved plant and cyperaceous plant.

The results are shown in Tables 165 and 166. In the tables, E.o. means Echinochloa oryzicola, M.v. means Monochoria vaginalis, and S.J. means Scirpus juncoides.

                  TABLE 165                                                        ______________________________________                                         Compound No.                                                                               E.o.         M.v.   S.j.                                           ______________________________________                                          3          5            5      4                                               9          5            5      3                                               15         4            5      3                                               52         4            5      5                                               55         5            5      5                                               68         4            5      3                                               72         5            5      4                                               83         4            4      4                                              109         5            5      4                                              152         4            5      4                                              698         5            5      5                                              706         5            5      5                                              709         5            5      4                                              783         5            5      5                                              806         5            5      5                                              842         5            5      5                                              866         5            5      2                                              872         5            5      5                                              885         5            5      4                                              888         5            5      5                                              897         5            5      3                                              902         5            5      5                                              920         5            5      4                                              921         5            5      3                                              938         5            5      5                                              ______________________________________                                    

                  TABLE 166                                                        ______________________________________                                         Compound No.                                                                               E.o.         M.v.   S.j.                                           ______________________________________                                          951        5            5      4                                               956        5            5      4                                               968        5            5      4                                               986        5            5      2                                               998        5            5      4                                              1006        5            5      3                                              1016        5            5      4                                              1025        5            5      4                                              1028        5            5      5                                              1030        5            5      5                                              1036        5            5      4                                              1046        5            5      4                                              1057        5            5      5                                              1058        5            5      5                                              1060        5            5      3                                              1066        5            5      5                                              ______________________________________                                    

Test Example 6

Growth inhibiting effect on weeds

As the test plants, Polygonum lapathifolium and Amaranthus viridis were used.

A square-shaped pot (7.1×7.1 cm) was charged with upland soil. The seeds (10 seeds/pot) of the above plants were sown on the soil and grown in a greenhouse for 7 days. Seven days after sowning, the test compound (20 g ai/a) was sprayed on the plant using a pressure-type sprayer.

Three weeks after spraying, the height of the plant was measured, and the growth inhibiting ratio was calculated according to the following equation: ##EQU2## The results are shown in Table 167. In the table, P.1. means Polygonum lapathifolium and A.v. means Amaranthus viridis.

                  TABLE 167                                                        ______________________________________                                         Compound No.      P.1.   A.v.                                                  ______________________________________                                         127               63     48                                                    863               52     66                                                    968               54     34                                                    970               57     48                                                    976               64     55                                                    1036              67     67                                                    1066              66     57                                                    ______________________________________                                     

What is claimed is:
 1. A compound of the formula (I): ##STR1403## wherein R¹ is selected from the group consisting of pyridyl, substituted pyridyl, pyridyl alkyl, and substituted pyridyl alkyl, wherein the alkyl group contains 1 to 4 carbon atoms; R² is selected from the group consisting of hydrogen, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, halogenated C₁₋₆ alkyl, halogenated C₂₋₆ alkenyl, halogenated C₂₋₆ alkynyl, C₃₋₈ cycloalkyl, phenyl, substituted phenyl, benzyl and substituted benzyl; R³ is selected from the group consisting of hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy and halogen; X is 0 or S; Y is CH or N; and ˜ represents any configuration of the E-isomer, Z-isomer or a mixture of E- and Z-isomers; wherein the substituted pyridyl, substituted pyridyl alkyl, substituted phenyl, and substituted benzyl have 1 to 5 substituents selected from the group consisting of C₁₋₅ alkyl, C₁₋₄ alkoxy, phenyl, phenoxy, benzyloxy, C₁₋₄ alkylthio, C₁₋₃ alkylsulfonyl, cyano, nitro, halogen, halogenated C₁₋ 3 alkyl, and halogenated C₁₋₃ alkoxy; or a salt thereof.
 2. A compound according to claim 1, wherein R¹ is 2-pyridyl or substituted 2-pyridyl, or a salt thereof.
 3. A compound according to claim 1, wherein R² is alkyl or C₂₋₆ alkenyl, or a salt thereof.
 4. A compound-according to claim 1, wherein R² is methyl, ethyl or allyl, or a salt thereof.
 5. A compound according to claim 1, wherein R³ is hydrogen, methyl, methoxy, fluorine or chlorine, or a salt thereof.
 6. A compound according to claim 1, wherein X is O, or a salt thereof.
 7. A compound according to claim 1, wherein Y is CH, or a salt thereof.
 8. A compound according to claim 1, wherein R¹ is pyridyl or substituted pyridyl; R² is C₁₋₆ alkyl; R³ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy or halogen; X is 0; and Y is CH; or a salt thereof.
 9. A compound according to claim 1, wherein R¹ is 5-trifluoromethyl-2-pyridyl, R² is ethyl, R³ is hydrogen, X is 0, and Y is CH, or a salt thereof.
 10. A compound according to claim 1, wherein R¹ is 5-trifluoromethyl-2-pyridyl, R² is methyl, R³ is hydrogen, X is 0, and Y is CH, or a salt thereof.
 11. A compound according to claim 1, wherein R¹ is 5-trifluoromethyl-2-pyridyl, R² is methyl, R³ is 5-chloro, X is 0, and Y is CH, or a salt thereof.
 12. A compound according to claim 1, wherein R¹ is 5-trifluoromethyl-2-pyridyl, R² is methyl, R³ is 5-fluoro, X is 0, and Y is CH, or a salt thereof.
 13. A compound according to claim 1, wherein R¹ is 3,5-dichloro-2-pyridyl, R² is methyl, R³ is 5-chloro, X is 0, and Y is CH, or a salt thereof.
 14. A fungicidal composition comprising as an active ingredient a compound according to claim 1, and an inert carrier or diluent.
 15. A herbicidal composition comprising as an active ingredient a compound according to claim 1, and an inert carrier or diluent.
 16. A growth inhibiting composition comprising as an active ingredient a compound according to claim 1, and an inert carrier or diluent. 